WO2010134524A1 - 金属錯体およびその利用 - Google Patents
金属錯体およびその利用 Download PDFInfo
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- WO2010134524A1 WO2010134524A1 PCT/JP2010/058360 JP2010058360W WO2010134524A1 WO 2010134524 A1 WO2010134524 A1 WO 2010134524A1 JP 2010058360 W JP2010058360 W JP 2010058360W WO 2010134524 A1 WO2010134524 A1 WO 2010134524A1
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- Prior art keywords
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- metal complex
- substituted
- light
- emission
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- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 256
- 239000003446 ligand Substances 0.000 claims abstract description 80
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- -1 diarylethene compound Chemical class 0.000 claims abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims description 126
- 239000000203 mixture Substances 0.000 claims description 80
- 238000005259 measurement Methods 0.000 claims description 74
- 238000004364 calculation method Methods 0.000 claims description 63
- 125000000623 heterocyclic group Chemical group 0.000 claims description 60
- 125000000217 alkyl group Chemical group 0.000 claims description 57
- 125000003545 alkoxy group Chemical group 0.000 claims description 47
- 125000003118 aryl group Chemical group 0.000 claims description 46
- 125000005843 halogen group Chemical group 0.000 claims description 45
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 43
- 238000000295 emission spectrum Methods 0.000 claims description 43
- 238000001228 spectrum Methods 0.000 claims description 42
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 41
- 230000001678 irradiating effect Effects 0.000 claims description 38
- 230000008569 process Effects 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 150000001988 diarylethenes Chemical class 0.000 claims description 20
- 150000001721 carbon Chemical group 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
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- 229910052761 rare earth metal Inorganic materials 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
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Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
- G03C1/735—Organo-metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- 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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/351—Metal complexes comprising lanthanides or actinides, e.g. comprising europium
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Definitions
- the present invention relates to a metal complex and use thereof, and more particularly, to a metal complex formed by coordination of photochromic molecules and use thereof.
- photochromic molecules are reversibly changed in molecular structure and physicochemical properties by their photochemical reactions (also called photochromic reactions), so that they can be incorporated into various molecules to cause chemical and physical changes.
- Research as a unit is actively conducted.
- As such an optical switching unit a metal complex having a photochromic molecule as a ligand has been reported.
- the emission characteristics of metal ions depend on the symmetry of the metal complex.
- a metal complex having a photochromic molecule as a ligand the symmetry of the metal complex is changed by a change in the molecular structure of the photochromic molecule.
- photoirradiation of photochromic molecules in a metal complex changes the molecular structure of the photochromic molecules, which changes the emission characteristics such as the emission intensity when a metal ion is excited using excitation light unique to the metal ion.
- the intensity of emitted light can be increased or attenuated using an optical signal.
- a metal complex having a photochromic molecule as a ligand for example, a complex having a ligand in which diarylethene as a photochromic molecule is incorporated in phenanthroline shown in FIG. 6 is complexed by ON / OFF switching of a ⁇ -conjugated system accompanying a photochromic reaction. Since it is possible to change the emission color by MLCT transition control, it has been reported that it may be applied as a molecular device (see Non-Patent Document 1).
- Non-Patent Document 2 reversible fluorescence switching using a fluorescence quenching effect associated with a photochromic reaction by introducing a photochromic site into phthalocyanine has been reported (see Non-Patent Document 2).
- the main recording layer made of a photochromic composition has a dye having an absorption at a wavelength longer than the absorption wavelength of the colored state of the photochromic material.
- An optical information recording medium containing the above is disclosed.
- Patent Document 2 discloses an optical information recording material that can develop a brown color such as brown alone and has a high interconversion speed between tautomers.
- the optical information recording media described in Patent Documents 1 and 2 realize optical recording with a single molecule, and do not relate to a metal complex having a photochromic molecule as a ligand.
- Patent Document 3 discloses a metal that is a material that does not transmit radiation in order to solve the problem that it is difficult to improve sensitivity due to the transmission of radiation when a photochromic compound is used in a color dosimeter.
- a metal complex is present in a specific ratio with respect to a photochromic compound.
- Patent Document 3 does not use a change in the light emission characteristics of metal ions caused by coordinate bonding of photochromic molecules to metal.
- Japanese Patent Publication Japanese Patent Laid-Open No. 7-77774 (published on March 20, 1995)” Japanese Patent Publication “Japanese Unexamined Patent Application Publication No. 2009-79132 (published on April 16, 2009)” Japanese Patent Publication “Japanese Patent Laid-Open No. 2002-285146 (published on October 3, 2002)”
- the present invention has been made in view of the above-described problems, and its purpose is to emit metal ions in a metal complex having a photochromic molecule as a ligand due to a change in the molecular structure accompanying a photochromic reaction of the ligand.
- the object is to provide a metal complex having a large change in properties.
- the present inventors have found that a diarylethene-based photochromic molecule is coordinated to a metal ion via two specific groups that are directly bonded to each reactive site carbon.
- the inventors have found that it is possible to provide a metal complex having a large change in light emission characteristics due to a change in molecular structure accompanying a photochromic reaction of a ligand, and completed the present invention. That is, the present invention includes the following inventions.
- the photochromic molecule is coordinated to a metal ion via two groups that are directly bonded to each reactive site carbon, and each of the groups is independently represented by the following formula group (1).
- a metal complex which is any group selected from the group consisting of:
- the photochromic molecule is represented by the following general formula (2)
- R 1 and R 2 each independently represents an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted aryl group;
- R 3 and R 4 are each independently a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted aryl group, or R 3 and R 4 form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring, Ring A represents a group X, a reaction point carbon bonded to the group X, and a hydrocarbon ring or a heterocycle formed with a carbon
- Ring B represents a hydrocarbon ring or a heterocyclic ring formed together with the group Y, the reaction point carbon bonded to the group Y, and the carbon atom adjacent to the reaction point carbon, and is the hydrocarbon ring or heterocycle a monocycle? Or further forms a condensed ring with one or more hydrocarbon rings or heterocyclic rings.
- the photochromic molecule is represented by the following general formula (3)
- the group X and the group Y each independently represent any group selected from a, b and c in the formula group (1)
- R 1 and R 2 each independently represents an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted aryl group
- R 3 and R 4 are each independently a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted aryl group, or R 3 and R 4 form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring
- D and E each independently represent any group selected from
- the group V and the group W each independently represent a group represented by d in the above formula group (1);
- R 1 and R 2 each independently represents an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted aryl group;
- R 3 and R 4 are each independently a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted aryl group, or R 3 and R 4 form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring, T and U each independently represent a carbon atom or
- the photochromic molecule is represented by the following general formula (5):
- R 1 and R 2 are each independently an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted aryl group.
- R 3 and R 4 are each independently a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted aryl group, or R 3 and R 4 form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.
- the metal complex according to any one of [1] to [3], which is a ligand having a structure represented by:
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each independent.
- the metal complex according to any one of [1] to [4], wherein the ligand having any structure selected from is further coordinated to the metal ion.
- R 1 and R 2 are each independently an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted aryl group.
- R 3 and R 4 are each independently a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted aryl group, or R 3 and R 4 form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring, R 11 and R 12 each independently represents an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group having 1 to 8 carbon atoms, or a phenyl group, M represents a metal ion, n represents an integer of 1 to 5, m represents an integer of 0 to 4, and the sum of n and m is 6 or less. ) A metal complex having a structure represented by:
- the trivalent ion is Ce 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Tb 3+ , Dy 3+ , Er 3+ , Pr 3+ , Tm 3+ or Yb 3+
- a composition comprising the metal complex according to any one of [1] to [9] and a medium.
- a recording for recording information on the photochromic molecule by irradiating the metal complex according to any one of [1] to [9] or the composition according to [10] with light having a wavelength ⁇ 1. Irradiating the metal complex or composition with light of wavelength ⁇ 3, receiving light emitted from the metal complex or composition, measuring the emission intensity of the emission, and based on the measured emission intensity of the emission And a reproducing step of reproducing the information recorded on the photochromic molecule.
- a second light emission measurement step for receiving light emitted from the light source and measuring the light emission spectrum of the light emission; and a calculation step for calculating the intensity of each light emission spectrum measured in the first light emission measurement step and the second light emission measurement step; ,
- the results obtained in the above calculation process Information identification method which comprises an identification step of identifying the Tagged identification information.
- the calculation step includes a first calculation substep for calculating a ratio of intensity of line spectra of a plurality of specific wavelengths among the emission spectra measured in the first emission measurement step, and the second emission measurement.
- the information identification method according to [14] wherein identification information associated with a ratio is identified, and identification information associated with a ratio calculated in the second calculation sub-step is further identified.
- the calculation step includes a first calculation substep for calculating a ratio of intensity of line spectra of a plurality of specific wavelengths among the emission spectra measured in the first emission measurement step, and the second emission measurement.
- the second calculation substep for calculating the ratio of the intensities of the line spectra of the plurality of specific wavelengths, the ratio calculated in the first calculation substep, and the second calculation sub
- a third calculation substep for calculating a ratio with the ratio calculated in the step, wherein the identification step identifies identification information associated with the ratio calculated in the third calculation substep.
- the diarylethene-based photochromic molecule is coordinated to the metal ion via two groups that are directly bonded to each reactive carbon, and the groups are independent of each other.
- a metal complex having a large change in the light emission characteristics of the metal ion due to a change in the molecular structure accompanying the photochromic reaction of the ligand. There is an effect that it can be provided. Therefore, it is possible to increase or attenuate the emitted light intensity using the optical signal, and it is possible to provide a highly sensitive optical switching unit.
- FIG. It is a figure which shows the emission spectrum of [Eu (BTFO4) (HFA) 3 ] concerning one Embodiment of this invention. It is the figure which normalized the emission spectrum of [Eu (BTFO4) (HFA) 3 ] concerning one Embodiment of this invention so that the emission intensity of 592nm may be set to 1.
- FIG. It is a figure which shows the absorption spectrum of [Eu (BTFO4) (HFA) 3 ] concerning one Embodiment of this invention.
- FIG. It is a figure which shows typically the characteristic of the metal complex concerning this invention, (a) is a figure which shows typically the transition of a diarylethene and a metal ion, (b) is a figure showing the function of a diarylethene and a metal ion typically.
- FIG. It is a figure which shows a prior art, Comprising: It is a figure which shows the photochromic reaction in the metal complex which the ligand which built diarylethene in phenanthroline coordinated. It is a figure which shows a prior art, Comprising: It is a figure which shows the photochromic reaction in the complex which introduce
- diarylethene-based photochromic molecules as ligands and directly bonded two specific groups to each reactive site carbon, through these groups. It has been found that, when coordinated to a metal ion, the emission intensity and the change due to the structural change of the ligand are remarkably increased.
- the metal complex according to the present invention is a metal complex in which a diarylethene-based photochromic molecule is coordinated to a metal ion, and the photochromic molecule is bonded to each reaction point carbon via two groups.
- the group is coordinated to a metal ion, and the group is any group independently selected from the following formula group (1).
- the “photochromic molecule” is a molecule having photochromic reactivity.
- Photochromic reactivity refers to the property that a single chemical species reversibly changes to two isomers with different absorption spectra by recombination of chemical bonds without changing the molecular weight by the action of light. Say. Therefore, since the two isomers of the photochromic molecule have different molecular structures, not only the absorption spectrum but also various molecular properties such as fluorescence characteristics, refractive index, and dipole moment are different.
- diarylethene-based photochromic molecule refers to a diarylethene-based photochromic molecule that undergoes a ring-closing / ring-opening reaction by the action of light, and a molecule having two reaction point carbons involved in the ring-closing / ring-opening reaction.
- a diarylethene-based photochromic molecule when irradiated with light having a specific wavelength ⁇ 1, a ring-closing reaction occurs between two reaction point carbons, and the ring-opening body changes to a ring-closing body. Subsequently, when light having a specific wavelength ⁇ 2 different from the wavelength ⁇ 1 is irradiated, a ring-opening reaction occurs between the two reaction point carbons, and the ring-closed body returns to the original ring-opened body.
- the wavelength ⁇ 1 and the wavelength ⁇ 2 are different wavelengths, and are wavelengths specific to the photochromic molecule.
- the molecular structure of the diarylethene-based photochromic molecule can be reversibly changed between a ring-closed body and a ring-opened body using light having wavelengths ⁇ 1 and ⁇ 2.
- the diarylethene compound has the advantages of excellent thermal irreversibility, high storage stability under light shielding, and excellent repeat durability.
- reaction point carbon refers to two carbon atoms involved in a ring-closing / ring-opening reaction by the action of light. That is, in the ring-closing reaction, the two carbon atoms are bonded, and in the ring-opening reaction, the bond between the two carbon atoms is opened.
- the diarylethene-based photochromic molecule is coordinated to the metal ion via two groups that are directly bonded to each reaction point carbon, and each of the groups is independently represented by the above formula group. It is any group selected from (1). That is, when the group is a and b, the photochromic molecule is coordinated to a metal atom via a sulfur atom and an oxygen atom, and when the group is c, the photochromic molecule is a carbon atom. When the group is d, the photochromic molecule is coordinated to the metal atom via a nitrogen atom and an oxygen atom.
- the structure of the metal complex according to the present invention has a structure in which a diarylethene-based photochromic molecule is coordinated to a metal ion.
- the metal ion includes a ligand other than the photochromic molecule (hereinafter, “other ligands”). May also be bonded.
- other ligands a ligand other than the photochromic molecule
- (I-1) photochromic molecule, (I-2) metal ion, (I-3) other ligand, (I-4) characteristics of the metal complex according to the present invention Details will be described in this order.
- the photochromic molecule is a diarylethene-based photochromic molecule, which is selected from any of the groups selected from the two formula groups (1) directly bonded to each reactive site carbon. Although it will not specifically limit if it is a photochromic molecule which can be coordinated to a metal ion, For example, following General formula (2)
- numerator which has a structure represented by can be used suitably.
- the group X and the group Y each independently represent any group selected from the above formula group (1).
- the photochromic molecule is coordinated to the metal ion through the group X and the group Y.
- R 1 and R 2 are each independently an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted group.
- An aryl group is shown.
- the alkyl group is more preferably a linear or branched alkyl group having 1 to 20 carbon atoms. Specific examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like. Can do.
- the alkoxyl group is more preferably a linear or branched alkoxyl group having 1 to 20 carbon atoms.
- Specific examples of the alkoxyl group include, for example, methoxy group, ethoxy group, propoxyl group, isopropoxyl group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, pentyloxy Groups and the like.
- the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- the fluorine-substituted alkyl group is more preferably a group in which at least one hydrogen atom of the alkyl group as described above is substituted with a fluorine atom, such as a trifluoromethyl group, a pentafluoroethyl group, etc. Can be suitably used.
- the aryl group is not particularly limited, but is preferably a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, or the like.
- Examples of the substituent when the aryl group is substituted include an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, and a carboxyl group.
- R 3 and R 4 are each independently a hydrogen atom, alkyl group, alkoxyl group, halogen atom, fluorine-substituted alkyl group, cyano group, hydroxyl group, carboxyl group, substituted or unsubstituted. Or R 3 and R 4 form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.
- R 3 and R 4 may be bonded to each other via a divalent group (L) to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.
- Such a hydrocarbon ring or heterocyclic ring is more preferably a 5-membered ring, 6-membered ring, 7-membered ring, 8-membered ring, etc., and may be aromatic or non-aromatic.
- the divalent group —R 3 — (L) —R 4 — forming the hydrocarbon ring is preferably a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms.
- divalent group —R 3 — (L) —R 4 — examples include, for example, a propylene group, a tetramethylene group, a hexamethylene group, a heptamethylene group, a pentenylene group, a hexenylene group, a peptenylene group, and the like. Can be mentioned.
- divalent group —R 3 — (L) —R 4 — forming the heterocyclic ring at least one of the carbon atoms of the hydrocarbon group is independently a nitrogen atom, an oxygen atom, or a sulfur atom.
- the divalent group -R 3- (L) -R 4- that forms a substituted hydrocarbon ring or a substituted heterocycle is not particularly limited as long as it has the above substituent. May be, for example, a fluorine-substituted alkylene group such as — (CF 2 ) n— (wherein n represents an integer of 3 to 20).
- ring A represents a hydrocarbon ring or a heterocycle formed together with a group X, a reaction point carbon bonded to the group X, and a carbon atom adjacent to the reaction point carbon, and the hydrocarbon
- the ring or heterocycle is a single ring or further forms a condensed ring with one or more hydrocarbon rings or heterocycles.
- the hydrocarbon ring or heterocyclic ring formed together with the group X, the reaction point carbon bonded to the group X, and the carbon atom adjacent to the reaction point carbon are particularly those containing the group a, b, c or d. Although not limited, it is more preferably a 5-membered or 6-membered aromatic ring.
- hydrocarbon ring or heterocyclic ring examples include benzene ring, thiophene ring, pyrrole ring, imidazole ring, pyrazole ring, isothiazole ring, isoxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring and the like. it can.
- the hydrocarbon ring or heterocyclic ring is also not particularly limited as one or more hydrocarbon rings or heterocyclic rings in the case where a condensed ring is formed with one or more hydrocarbon rings or heterocyclic rings. Alternatively, it may be a single ring or a condensed ring.
- Examples thereof include a benzene ring, naphthalene ring, anthracene ring, thiophene ring, pyrrole ring, imidazole ring, pyrazole ring, isothiazole ring, isoxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring and the like.
- ring B represents a hydrocarbon ring or a heterocycle formed together with a group Y, a reaction point carbon bonded to the group Y, and a carbon atom adjacent to the reaction point carbon, and the hydrocarbon
- the ring or heterocycle is a single ring or further forms a condensed ring with one or more hydrocarbon rings or heterocycles.
- a hydrocarbon ring or heterocycle formed together with the group Y, the reaction point carbon bonded to the group Y, and the carbon atom adjacent to the reaction point carbon, and the hydrocarbon ring or heterocycle further comprises one or more hydrocarbon rings
- one or more hydrocarbon rings or heterocyclic rings in the case of forming a condensed ring with the heterocyclic ring are the same as those in the case of the ring A, and thus description thereof is omitted here.
- a ligand having a structure represented by can be suitably used.
- the group X and the group Y each independently represent any group selected from a, b and c in the formula group (1).
- D and E each independently represent a carbon atom or a nitrogen atom
- R 5 and R 6 each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom, or a fluorine-substituted group.
- Alkyl group, cyano group, hydroxyl group, carboxyl group, substituted or unsubstituted aryl group, or R 5 and R 6 form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring is doing.
- R 7 and R 8 are each independently a hydrogen atom, alkyl group, alkoxyl group, halogen atom, fluorine-substituted alkyl group, cyano group, hydroxyl group, carboxyl group, substituted or unsubstituted aryl group, or , R 7 and R 8 form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.
- alkyl group, alkoxyl group, halogen atom, fluorine-substituted alkyl group, and substituted or unsubstituted aryl group are the same as in the case of R 1 and R 2 .
- a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle formed by R 5 and R 6 , a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle, and R 7 and R 8
- the substituted or unsubstituted hydrocarbon ring or the substituted or unsubstituted heterocyclic ring is not particularly limited, and may be a single ring or a condensed ring.
- Examples include benzene ring, naphthalene ring, anthracene ring, thiophene ring, pyrrole ring, imidazole ring, pyrazole ring, isothiazole ring, isoxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring and the like.
- R 1 and R 2 , and R 3 and R 4 are as described in the general formula (2), and thus description thereof is omitted here.
- a ligand having a structure represented by can also be suitably used.
- the group V and the group W each independently represent a group represented by d in the above formula group (1).
- T and U each independently represent a carbon atom or a sulfur atom
- R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom, or a fluorine atom.
- alkyl group, alkoxyl group, halogen atom, fluorine-substituted alkyl group, and substituted or unsubstituted aryl group are the same as in the case of R 1 and R 2 .
- R 1 and R 2 , and R 3 and R 4 are the same as described in the general formula (2), and thus the description thereof is omitted here.
- the photochromic molecule as a more specific example, for example, the following general formula (5)
- numerator which has a structure represented by can be used suitably.
- R 1 and R 2 each independently represent an alkyl group, an alkoxyl group, a halogen atom, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted aryl group. Show.
- R 3 and R 4 are each independently a hydrogen atom, alkyl group, alkoxyl group, halogen atom, fluorine-substituted alkyl group, cyano group, hydroxyl group, carboxyl group, substituted or unsubstituted aryl group, or , R 3 and R 4 form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.
- the number of coordination of the photochromic molecule with respect to the metal ion is not particularly limited. That is, only one photochromic molecule described above may be coordinated to the metal ion, or a plurality of photochromic molecules may be coordinated to the metal ion.
- the photochromic molecules may all be the same, or a plurality of different types of photochromic molecules may be combined and coordinated. It may be.
- the metal ion used in the metal complex according to the present invention is not particularly limited.
- group 1A Li, Na, K, Rb, Cs, Fr
- group 1A Li, Na, K, Rb, Cs, Fr
- 2A group Be, Mg, Ca, Sr, Ba, Ra
- 3A group Sc, Y
- 4A group Ti, Zr, Hf
- 5A group V, Nb, Ta
- 6A group Cr, Mo, W
- Group 7A Mn, Tc, Re
- Group 8 Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- Group 1B Cu, Ag, Au
- Group 2B Zn, Cd, Hg
- lanthanoid series La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
- actinoid series Ac, Th, Pa, U, Np, Pu,
- the rare earth ions include the 3A group (Sc, Y) and the lanthanoid series (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu).
- a trivalent lanthanoid ion is more preferable from the viewpoint that stronger light emission can be obtained. Similar effects can also be obtained when the present invention is applied to such a technique. That is, when rare earth ions are used in the present invention, trivalent lanthanoid ions are more preferable in that stronger light emission can be obtained.
- Ce 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Tb 3+ , Dy 3+ , Er 3+ , Pr 3+ , Tm 3+ , Yb 3+ are particularly preferable.
- the excitation wavelength, emission intensity, and emission wavelength of the metal complex can be changed by changing the metal ion.
- the excitation wavelength, emission intensity, and emission wavelength of the metal complex according to the present invention can be changed by changing the photochromic molecule or changing the combination of the metal ion and the photochromic molecule.
- a ligand other than the photochromic molecule may be coordinated with the metal ion.
- ligands include pyridine and derivatives thereof; nitrogen-containing heterocycles and derivatives thereof other than pyridine; ethylenediamine, nitro, cyano and derivatives thereof; ketones and derivatives thereof; sulfonyl and derivatives thereof; Compounds and derivatives thereof; and phosphine oxides and derivatives thereof.
- Examples of the pyridine and derivatives thereof include the following general formula group (9)
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently an alkyl group, an alkoxyl group, a halogen atom, trifluoromethyl.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently an alkyl group, an alkoxyl group, a halogen atom, trifluoromethyl.
- nitrogen-containing heterocycle other than pyridine and derivatives thereof include, for example, the following general formula group (10)
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each independently An alkyl group, an alkoxyl group, a halogen atom, a trifluoromethyl group, a fluorine-substituted alkyl group, a cyano group, a hydroxyl group, a carboxyl group, a sulfonyl group, an aryl group or a substituted aryl group, or between adjacent substituents , Are linked together to form a carbocycle, heterocycle, substituted carbocycle, or substituted heterocycle.
- ethylenediamine, nitro, cyano and derivatives thereof include, for example, the following general formula group (11)
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently an alkyl group, an alkoxyl group, a halogen atom, trifluoromethyl.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently an alkyl group, an alkoxyl group, a halogen atom, trifluoromethyl.
- ketone and derivatives thereof include the following general formula group (12)
- R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently an alkyl group, an alkoxyl group, a halogen atom, a trifluoromethyl group, or a fluorine-substituted alkyl group.
- R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group having 1 to 8 carbon atoms, or a phenyl group.
- R 1 , R 2 , R 3 , R 4 , and R 5 are each independently an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group having 1 to 8 carbon atoms, or It is a phenyl group.
- phosphine oxide and derivatives thereof include the following general formula group (15)
- R 1 , R 2 , R 3 , and R 4 are each independently an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group having 1 to 8 carbon atoms, or a phenyl group. is there.
- the synthesis of the metal complex according to the present invention can be facilitated, the solubility in a solvent can be increased, and the stability of the metal complex can be increased.
- Examples of the metal complex according to the present invention in which the above photochromic molecule and other ligands are coordinated to a metal ion include, for example, the following general formula (7)
- the metal complex which has a structure represented by these can be mentioned.
- R 1 and R 2 , and R 3 and R 4 are the same as described in the general formula (2), and thus the description thereof is omitted here.
- R 11 and R 12 each independently represents an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group having 1 to 8 carbon atoms, or a phenyl group.
- the alkyl group having 1 to 8 carbon atoms may be linear or branched.
- the fluorine-substituted alkyl group having 1 to 8 carbon atoms is not particularly limited.
- a perfluoromethyl group for example, a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group,
- a perfluoroalkyl group such as a perfluoropeptyl group or a perfluorooctyl group can be preferably used.
- M represents a metal ion
- n represents an integer of 1 to 5. It is preferable that n is 1 to 5 because the effects of the present invention can be effectively expressed. M represents an integer of 0 to 4. It is preferable that m is 0 to 4 because the metal ions can correspond to 0 to 4 valences.
- the sum of n and m is preferably 6 or less. Since the sum of n and m is 6 or less, the coordination structure is preferably 12 or less.
- the method for producing such a metal complex according to the present invention is not particularly limited, and a suitable production method is appropriately selected from conventionally known methods according to the ligand coordinated to the metal complex, What is necessary is just to use in combination.
- the emission characteristics of the metal ions when excited with the light with the wavelength ⁇ 3 are different between after irradiation with the light with the wavelength ⁇ 1 and after irradiation with the light with the wavelength ⁇ 2. .
- difference in light emission characteristics means that the properties of light emission components, in other words, the parity is different.
- the emission characteristics of metal ions are different means that the relative intensity of the emission intensity of the electric dipole transition is different from the emission intensity of the magnetic dipole transition.
- the metal complex concerning this invention has the characteristic that the light emission characteristic of the metal ion by the structure change of a ligand by the said structure, especially the light emission intensity and the light emission intensity change are remarkably large.
- the emission characteristics of metal ions that change due to changes in the structure of the ligand are not limited to the emission intensity, but the emission rate calculated from the emission quantum yield, emission lifetime, emission quantum yield, and emission lifetime. Constants are also included in the light emission characteristics.
- the light having the wavelength ⁇ 1 is emitted from the metal complex according to the present invention by evaluating the light emission characteristics when the metal ions are irradiated with light having the wavelength ⁇ 3. It is possible to determine with high sensitivity whether the structure is when irradiated or the structure when irradiated with the wavelength ⁇ 2.
- the emission intensity when excited with light of wavelength ⁇ 3 is greatly changed by irradiation with light of wavelength ⁇ 1 or wavelength ⁇ 2. That is, according to the metal complex concerning this invention, it becomes possible to amplify or attenuate light using light. Therefore, the metal complex according to the present invention can be applied as a high-speed switch to a control system of an optical amplification device.
- the photochromic molecule of the metal complex according to the present invention changes to a different molecular structure by irradiation with light of wavelength ⁇ 1 and wavelength ⁇ 2. This change in molecular structure causes the photochromic molecule to have absorption bands at different wavelengths.
- the metal complex of the present invention when the absorption spectrum when the molecular structure of the photochromic molecule was reversibly changed by irradiation with light of wavelength ⁇ 1 and wavelength ⁇ 2, all of the metal complexes having different molecular structures were measured. Unexpected results were obtained that had an absorption band at a wavelength lower than the wavelength of the excitation light of the metal ion.
- the present inventors have proposed a “photochromic rare earth complex” in which a photochromic molecule and a rare earth complex are combined as shown in FIG.
- the absorption band of the photochromic rare earth complex changed from a ring-opened body to a ring-closed body by UV irradiation is around 600 nm
- Eu (III) Since it overlapped with the readout wavelength and the emission wavelength, irradiation with “reading light” returns to the chemical structure (ring opening) before irradiation with “writing light”, and complete nondestructive readout has not been realized.
- the absorption band (writing, erasing) based on the photochromic molecule and the absorption band of the metal complex that is, the wavelength of the excitation light (reading out).
- the emission wavelength of the metal complex memory detection
- the metal complex according to the present invention can input and write (or record) information and signals to the photochromic molecule with light of wavelength ⁇ 1.
- information or signals input or recorded in the photochromic molecule can be output or read (or reproduced) by using light of wavelength ⁇ 3.
- information or signals input or recorded in the photochromic molecule can be erased.
- the wavelengths ⁇ 1, ⁇ 2, and ⁇ 3 are different from each other, and the absorption band based on the photochromic molecule is different from the emission wavelength of ⁇ 3 and the metal complex, so that information, signal input, recording, output, reproduction, and erasure can be performed. They do not buffer each other. Therefore, the metal complex according to the present invention can be used as an information recording medium, a nonvolatile memory, and a switching element.
- the metal complex according to the present invention is an independent photochromic molecule that is an optical information recording unit and a metal ion that is an optical information transmission unit. .
- the photochromic molecule and the metal ion each independently respond to light.
- the metal complex according to the present invention is irradiated with light having a wavelength ⁇ 1
- the molecular structure of the photochromic molecule that is an optical information recording portion is changed from a ring-opened body to a ring-closed body by a photochromic reaction.
- the photochromic molecule whose molecular structure has been changed that is, the photochromic molecule of the closed ring, returns to the original molecular structure, that is, the ring-opened body.
- the wavelength ⁇ 1 and the wavelength ⁇ 2 are different wavelengths, and are wavelengths specific to the photochromic molecule.
- the molecular structure can be reversibly changed between the ring-opened body and the ring-closed body using the light with the wavelengths ⁇ 1 and ⁇ 2.
- the photochromic molecule does not respond to light having a wavelength ⁇ 3. That is, since the wavelength ⁇ 3 for detecting the light emission of the metal complex is different from the absorption wavelength of the photochromic molecule, the light having the wavelength ⁇ 3 does not induce a change in the molecular structure of the photochromic molecule.
- the metal ion which is an optical information transmitter does not respond to light having wavelength ⁇ 1 or wavelength ⁇ 2. That is, the metal ion is excited by light having the wavelength ⁇ 1 or ⁇ 2, and does not emit light.
- the wavelength ⁇ 3 is different from the wavelengths ⁇ 1 and ⁇ 2.
- the structure of the photochromic molecule is changed by “writing light” (wavelength of ⁇ 1).
- the ligand field of the metal ion coordinated by the photochromic molecule is changed. Since the light emission characteristics of the metal ions change due to this change in the ligand field, optical information can be read by detecting the light emission characteristics change with light different from the absorption wavelength of the photochromic molecule.
- the light of wavelength ⁇ 1, wavelength ⁇ 2, and wavelength ⁇ 3 is not limited to light of a single wavelength, but may be light of a specific wavelength range.
- the wavelength ⁇ 1, the wavelength ⁇ 2, and the wavelength ⁇ 3 are values that vary depending on the metal ions and photochromic molecules to be used and are not limited thereto.
- ⁇ 1 is 200 to 600 nm
- the wavelength ⁇ 2 is 350 to 800 nm.
- the wavelength ⁇ 3 is 450 to 1000 nm.
- the wavelength of the absorption band of the metal complex having a different molecular structure in which the molecular structure of the photochromic molecule is reversibly changed by irradiation with light having wavelengths ⁇ 1 and ⁇ 2 is not particularly limited.
- the wavelength is preferably lower than the wavelength ⁇ 3.
- the metal complex according to the present invention has the following performance.
- the structure of the metal complex according to the present invention reversibly changes between two states by inducing a photochromic reaction using light of wavelength ⁇ 1 or ⁇ 2.
- the light irradiation method for inducing the photochromic reaction is not particularly limited as long as it can irradiate light having the wavelength ⁇ 1 or ⁇ 2.
- the structure of the photochromic molecule can be changed by irradiating light of a desired wavelength using a light source such as an LED, deuterium or xenon, a halogen lamp, or a laser.
- the metal complex according to the present invention emits light by being excited with light having a wavelength ⁇ 3, and is irradiated with light having a wavelength ⁇ 1 and after irradiation with light having a wavelength ⁇ 2.
- the emission characteristics of luminescence emitted by excitation with different light are different.
- the method of irradiating the light for exciting the metal complex according to the present invention is not particularly limited as long as it can irradiate the light having the wavelength ⁇ 3.
- the metal ions can be emitted by irradiating desired excitation light using an excitation light source such as an LED, deuterium, xenon, or halogen lamp.
- the change in the molecular structure of the photochromic molecule is not induced by the light of wavelength ⁇ 3 for detecting the light emission of the metal complex. Therefore, even if the light of wavelength ⁇ 3 is continuously irradiated, the light emission characteristics such as the light emission intensity do not change, and it is possible to read information written nondestructively.
- the light emission characteristics such as the light emission intensity can be changed depending on the irradiation intensity and irradiation time of the light of wavelength ⁇ 1 for writing.
- composition according to the present invention is a composition containing the above-described metal complex according to the present invention and a medium.
- the above-described composition may contain the above-described metal complex according to the present invention alone, or a mixture of plural kinds of metal complexes.
- the content of the metal complex according to the present invention is not particularly limited, and is appropriately set according to the use and the type of the medium.
- the composition according to the present invention contains the metal complex according to the present invention. Therefore, the composition according to the present invention exhibits specific photoresponsiveness with respect to three different wavelengths (wavelength ⁇ 1, wavelength ⁇ 2, wavelength ⁇ 3). Specifically, the composition according to the present invention emits light when irradiated with light having a wavelength ⁇ 3. This is because the metal ions of the metal complex contained in the composition are excited and emitted by irradiation with light having a wavelength ⁇ 3. In the composition according to the present invention, the light emission characteristics of the light emitted by irradiation with light of wavelength ⁇ 3 can be reversibly changed by using light of wavelengths ⁇ 1 and ⁇ 2. This is because the molecular structure of the photochromic molecule of the metal complex contained in the composition is reversibly changed by the photochromic reaction induced by the light having the wavelengths ⁇ 1 and ⁇ 2.
- the composition according to the present invention can change the light emission characteristics, in other words, the light emission intensity, using the light having the wavelength ⁇ 1 or the wavelength ⁇ 2. That is, the composition according to the present invention can amplify or attenuate light at high speed using light. Therefore, the composition according to the present invention can be used as a switching element such as a high-speed switch. Such a switching element can also be applied to a control system of an optical amplifying device. That is, application to optical information communication is also possible.
- the metal complex according to the present invention is different in the absorption band (writing, erasing) based on the photochromic molecule from the absorption band of the metal complex, that is, the wavelength of excitation light (reading) and the emission wavelength of the metal complex (memory detection). It is possible to read the optically recorded information without destroying it.
- the composition according to the present invention can be used very suitably for an information recording medium for recording or storing information and signals.
- the composition according to the present invention can be used for an information identification medium such as an ID card by utilizing the light emission characteristics of the composition according to the present invention and the characteristics in which the light emission characteristics are changed by a photochromic reaction.
- the metal complex according to the present invention has different light emission characteristics and photochromic reactivity depending on the type of photochromic molecules and metal ions constituting the metal complex. Therefore, the metal complex according to the present invention can function as a code. This code can be deciphered based on the light emission characteristics of the metal complex and the change in the light emission characteristics due to the photochromic reaction. Therefore, the composition containing the metal complex according to the present invention as a code can be used as an information identification medium.
- the medium contained in the composition according to the present invention is not particularly limited, and a suitable medium may be appropriately selected and used according to the use of the composition.
- the medium include organic solvents, resins, inorganic materials, and organic-inorganic hybrid materials.
- organic solvent examples include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, diethylbenzene, and isopropylbenzene; aliphatic hydrocarbon solvents such as alkanes and cycloalkanes; Halogenated hydrocarbon solvents such as 1,2-dichloroethane, tetrachloroethane, trichloroethylene, methyl iodide, chloroform, carbon tetrachloride, chlorobenzene, dichloronaphthalene; acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone Ketone solvents such as cyclohexanone; ether solvents such as diethyl ether, dimethoxyethane, diethoxyethane, tetrahydro
- polyimide resin polyamide resin, polymethyl methacrylic resin, polyacrylate, polystyrene resin, polyethylene naphthalate resin, polyester resin, polyurethane, polycarbonate resin, epoxy resin, polyethylene terephthalate resin
- vinyl chloride resins vinylidene chloride resins, acrylonitrile butadiene styrene (ABS) resins, acrylonitrile styrene (AS) resins, cycloolefin resins, siloxane polymers, and halides or deuterides thereof.
- ABS acrylonitrile butadiene styrene
- AS acrylonitrile styrene
- cycloolefin resins siloxane polymers
- halides or deuterides thereof may be used alone or in combination of two or more.
- examples of the inorganic material include glass produced by a sol-gel method.
- the medium as exemplified above can be used, but it is preferable to use a medium having high compatibility with the metal complex according to the present invention.
- an additive for imparting a specific function may be further added to the composition according to the present invention in accordance with its use.
- additives include additives such as antioxidants, inorganic fillers, stabilizers, antistatic agents, dyes, pigments, flame retardants, inorganic fillers, and elastomers for improving impact resistance. it can.
- additives such as a lubricant can be added.
- a leveling agent may be added to the composition according to the present invention.
- antioxidants examples include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethylphenylmethane. Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl-benzene, stearyl- ⁇ - (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-diethylphenylmethane, 3,9-bis [1,1-dimethyl-2- [ ⁇ - (3-t-butyl-4- Hydroxy
- examples of the inorganic filler include calcium carbonate, carbon fiber, and metal oxide.
- leveling agent examples include a fluorine-based nonionic surfactant, a special acrylic resin leveling agent, and a silicone leveling agent.
- the shape of the composition according to the present invention is not particularly limited, and may be any shape.
- Examples of the shape include a film shape, a plate shape, a powder shape, a granular shape, a granular shape, a paste shape, a liquid shape, and an emulsion.
- the method for producing the composition according to the present invention is not particularly limited, and a suitable method may be selected as appropriate according to the composition, shape, application, and the like.
- a suitable method may be selected as appropriate according to the composition, shape, application, and the like.
- the metal complex according to the present invention, the medium, and other additives as exemplified above as necessary may be added using a twin screw extruder, a brabender, a roll kneader, or the like. It can be produced by a method of mixing and pelletizing using an extruder, or a method of further pulverizing pellets with a pulverizer to form a powder.
- the metal complex according to the present invention when the composition is in a liquid state, the metal complex according to the present invention, the medium, and, if necessary, other additives as exemplified above are dissolved or dispersed in an appropriate solvent. Can be manufactured.
- the composition according to the present invention includes, for example, a high-speed switching element that can be used in an optical amplification method described later; a memory element that can be suitably used in an information recording / reproducing method described later; an information recording medium or an optical memory; In order to manufacture an information identification medium such as an ID card that can be suitably used, it can be preferably used.
- Such an information recording medium include an information recording medium in which a recording layer is formed on both sides or one side of a substrate.
- the recording layer may contain the composition according to the present invention.
- the thickness of the recording layer is preferably 0.01 ⁇ m to 3.0 mm, more preferably 0.05 ⁇ m to 1.0 mm.
- the thickness of the recording layer is less than 0.01 ⁇ m, the recording display performance of the recording layer may not be sufficiently exhibited.
- the thickness of the recording layer exceeds 3.0 mm, it may be difficult to form a smooth recording layer over the entire surface.
- the substrate examples include polymethyl methacrylic resin, polystyrene resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polycarbonate resin, polyamide resin, vinyl chloride resin, vinylidene chloride resin, acrylonitrile butadiene styrene ( An ABS resin, an acrylonitrile styrene (AS) resin, a thermoplastic resin such as a cycloolefin resin, glass, paper, or the like can be used.
- polymethyl methacrylic resin polystyrene resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polycarbonate resin, polyamide resin, vinyl chloride resin, vinylidene chloride resin, acrylonitrile butadiene styrene ( An ABS resin, an acrylonitrile styrene (AS) resin, a thermoplastic resin such as a cycloolefin resin, glass, paper, or the like can be used.
- ABS resin an
- the method for producing such an information recording medium is not particularly limited. For example, it is produced by casting a solution of the composition according to the present invention on the substrate and forming a recording layer on the substrate by subjecting the obtained solution layer to a solvent removal treatment. be able to.
- the method for casting the composition on a substrate is not particularly limited, and can be performed using a conventionally known method such as a bar coater.
- a coating film of the composition according to the present invention can also be produced by forming a coating film of the composition according to the present invention on the surface of the substrate.
- the method for forming the coating film of the composition according to the present invention on the surface of the substrate is not particularly limited, and a conventionally known method can be used.
- brush coating method, dip coating method, spray coating method, plate coating method, spinner coating method, bead coating method, wet coating method such as curtain coating method, gravure printing method, screen printing method, offset printing method, letterpress printing method, etc. can be mentioned.
- the information recording medium can be produced by molding the composition according to the present invention so that the substrate and the recording layer are integrally formed, or a film made of the composition according to the present invention can be formed on the substrate. It can also be manufactured by laminating. Specifically, for example, the information recording medium can be produced by molding the composition as a composition obtained by mixing the metal complex according to the present invention and the resin exemplified as the medium. In the information recording medium, a surface protective film or the like may be provided on the recording layer.
- composition according to the present invention can be used in the form of a liquid.
- a solution-like composition according to the present invention in which the metal complex according to the present invention is dissolved in an appropriate solvent (for example, a solvent exemplified as being usable in production) in a glass cell or the like information is obtained. It can be used as a recording medium.
- the high-speed switching element and the information identification medium can be manufactured by appropriately selecting a method suitable for each.
- the metal complex according to the present invention can amplify light at high speed by light. Therefore, the present invention also includes a light intensity adjustment method using the metal complex according to the present invention. Furthermore, the present invention includes an optical switch used in the method and an optical amplifying apparatus including the optical switch.
- the optical switch according to the present invention only needs to contain the metal complex according to the present invention, and other configurations and shapes are not particularly limited. Such an optical switch can be manufactured by using the composition according to the present invention.
- the light intensity adjustment method according to the present invention will be described in detail.
- the intensity of light emitted from the metal complex is changed to a wavelength ⁇ 1.
- Any other specific configuration is not particularly limited as long as it is a control method using light of wavelength ⁇ 2.
- the light intensity adjusting method is a method of amplifying or attenuating light with light based on the characteristics of the metal complex according to the present invention described above.
- the light intensity adjusting method according to the present invention light is amplified or attenuated by light, so that the light can be amplified or attenuated at a very high speed. Therefore, the light intensity adjusting method according to the present invention can be used for a control system of an optical amplifying apparatus. That is, it can be applied to high-speed switching of optical information communication.
- the present invention includes an information recording / reproducing method using the metal complex according to the present invention. Further, the present invention includes an information recording medium and a molecular memory used for the method, and an information recording / reproducing apparatus for performing the method.
- the information recording medium and the molecular memory according to the present invention can be manufactured by processing the composition according to the present invention.
- the information recording / reproducing method according to the present invention will be described in detail.
- the information recording / reproducing method includes a step of recording information on the photochromic molecule by irradiating light having a wavelength ⁇ 1 to a metal complex having a structure in which the photochromic molecule is coordinated to a metal ion (hereinafter, “ Recording step)), and irradiating the metal complex with light of wavelength ⁇ 3, receiving light emitted from the metal complex, measuring the emission intensity of the emission, and based on the measured emission intensity of the emission.
- Recording step a step of reproducing the information recorded on the photochromic molecule
- production step a step of reproducing the information recorded on the photochromic molecule, and other specific configurations are not particularly limited.
- the information recording / reproducing method further includes a step of erasing information recorded on the photochromic molecule by irradiating the metal complex with light having a wavelength ⁇ 2 (hereinafter referred to as “photochromic molecule”). , Also referred to as “erasing step”).
- photochromic molecule a wavelength ⁇ 2
- (IV-1) Recording Step the metal complex according to the present invention is irradiated with light having a wavelength ⁇ 1, and the structure of the photochromic molecule in the metal complex is changed from a ring-opened body to a ring-closed body. By utilizing this structural change, information can be recorded in the photochromic molecule.
- the photochromic of the metal complex according to the present invention at the irradiated portion of the information recording medium is irradiated by irradiating the recording layer with light having a wavelength ⁇ 1. Change the molecular structure and record information.
- the wavelength ⁇ 1 is not particularly limited, and is determined by the type of the photochromic molecule. Preferably, light in the ultraviolet region is used.
- the method for irradiating light with wavelength ⁇ 1 in the recording step is not particularly limited. For example, a method using a deuterium lamp, a xenon lamp, a mercury lamp, a halogen lamp, an LED, a laser, or the like can be given.
- the time for irradiating the metal complex with light having a wavelength ⁇ 1 is not particularly limited.
- irradiation may be performed for 1 picosecond or longer.
- (IV-2) Regeneration Step the metal complex according to the present invention is irradiated with light having a wavelength ⁇ 3 to cause the metal complex to emit light. Then, the emission intensity of the emitted light is measured, and the information recorded in the photochromic molecule in the recording step is reproduced based on the emission intensity. More specifically, in the reproduction step, first, the metal complex on which information is recorded in the recording step is irradiated with light having a wavelength ⁇ 3. Thereby, the metal complex is excited and emits light. Next, in the regeneration step, the emission intensity of the emitted light is measured. Then, based on the measured emission intensity, it is determined whether the photochromic molecule of the metal complex is a ring-opened body or a ring-closed body. Thereby, the information recorded on the metal complex is reproduced.
- each metal complex molecule in the irradiated portion of the information recording medium is irradiated by irradiating the recording layer with light of wavelength ⁇ 3.
- the luminescence intensity is measured.
- the wavelength ⁇ 3 is not particularly limited, and is determined by the type of the metal ion.
- the method of irradiating light with the wavelength ⁇ 3 in the reproduction step is not particularly limited. For example, a method using a deuterium lamp, a xenon lamp, a mercury lamp, a halogen lamp, an LED, a laser, or the like can be given.
- the time for irradiating the metal complex with light having a wavelength ⁇ 3 is not particularly limited.
- irradiation may be performed for 1 picosecond or longer.
- “measuring the emission intensity of emitted light” means measuring the intensity of the entire emission that has not been spectrally measured, measuring the intensity of the spectral emission spectrum, and having a specific wavelength of the spectral emission spectrum. It is meant to include all of measuring only the intensity of the line spectrum. That is, in the regeneration step, the intensity of the entire emission may be measured without dispersing the emission from the metal complex, or the intensity of the emission spectrum obtained by separating the emission may be measured, or the spectrum is dispersed. Only the intensity of the line spectrum of a specific wavelength of the emission spectrum may be measured.
- the configuration of the apparatus for measuring the light emission intensity can be simplified and the time required for the regeneration step can be shortened. If the intensity of the emission spectrum obtained by separating the emitted light is measured, the accuracy of identifying information can be improved. Furthermore, if only the intensity of the line spectrum of a specific wavelength of the spectral emission spectrum is measured, the apparatus configuration for measuring the emission intensity can be simplified, and at the same time, the time required for the regeneration process can be reduced. Further, the accuracy of identifying information can be improved.
- the number of wavelengths to be selected is not particularly limited, and may be one or may be two or more.
- the accuracy of reproducing information can be further improved. For example, if two wavelengths are selected, the ratio of the line spectrum intensities of the two wavelengths is used to determine whether the structure of the photochromic molecule of the metal complex is an open ring or a closed ring. be able to. Therefore, information can be reproduced with higher accuracy. If two wavelengths are selected, the time required for the regeneration process can be shortened. Therefore, information can be read out at higher speed.
- the wavelength to be selected may be appropriately selected according to the light emission characteristics of the type of metal complex or information identification medium to be used, and is not particularly limited.
- the wavelength of light emission by magnetic dipole transition or light emission by electric dipole transition can be selected.
- the wavelength of the light emission by the said magnetic dipole transition and the light emission by an electric dipole transition is determined by the kind of metal complex.
- the structure of the photochromic molecule is determined, for example, by comparing the luminescence intensity measured in the regeneration step with the luminescence intensity associated with the ring-opened body and the luminescence intensity associated with the ring-closed body. Can be done.
- “compare emission intensity” means that the intensity of the entire emission from the metal complex is measured in the regeneration step, and the emission intensity is associated with the ring-opened substance. It means that the intensity is compared with the emission intensity associated with the closed ring.
- “compare emission intensity” means that a plurality of line spectra measured in the regeneration process are measured. This means that each intensity is compared with each intensity of the line spectrum associated with the ring-opened body and the line spectrum associated with the ring-closed body.
- calculate the ratio of the intensity of the line spectrum measured in the reproduction step It means that the ratio is compared with the ratio associated with the ring-opened body and the ratio associated with the ring-closed body. According to the latter, the reproduction speed can be increased and at the same time the reproduction accuracy can be increased.
- the ratio when the ratio of line spectrum intensities is calculated, the ratio may be the ratio of the intensity of two line spectra, or the ratio of the intensity of three or more line spectra. Also good. By calculating the ratio of the intensity of more line spectra, the reproduction accuracy can be improved.
- the information recorded in the photochromic molecule is reproduced based on the emission quantum yield, emission lifetime, emission rate constant calculated from the emission quantum yield and emission lifetime, or a combination of two or more of these. May be. That is, the metal complex according to the present invention is irradiated with light having a wavelength of ⁇ 3 to cause the metal complex to emit light, and at least one of the emission quantum yield and emission lifetime of the emission is measured. Information recorded on the photochromic molecule is reproduced based on at least one of the emission lifetime and the radiation rate constant. A more specific reproduction method is the same as in the case of performing reproduction based on the emission intensity. In addition, the measuring method of a light emission quantum yield and the light emission lifetime is not specifically limited. Further, the measurement of the luminescence quantum yield may be performed by an absolute method or a relative method.
- the radiation rate constant is calculated using the following formulas (1) and (2) from the emission quantum yield and the emission lifetime.
- the information recorded in the photochromic molecule is the emission rate constant calculated from the above-mentioned emission intensity, combination of plural emission intensity, emission quantum yield, emission lifetime, emission quantum yield and emission lifetime.
- playback may be performed based on a combination of two or more of these. Thereby, the reproduction accuracy can be further improved.
- the metal complex or the information recording medium according to the present invention since the metal complex or the information recording medium according to the present invention is used, the metal complex is irradiated with light having a wavelength ⁇ 2, and the structure of the photochromic molecule is changed from a closed ring to an open ring. As long as it is not changed, information is not erased from the metal complex or the information recording medium. Therefore, the information recorded on the metal complex or the information recording medium can be reproduced repeatedly.
- (IV-3) Erasing Step the metal complex according to the present invention is irradiated with light having a wavelength of ⁇ 2, and the structure of the photochromic molecule in the metal complex is changed from a closed ring to an open ring.
- the structure of the photochromic molecule in the metal complex is changed from a closed ring to an open ring.
- the structure of the photochromic molecule can be erased.
- the entire recording layer can be erased by irradiating light having a wavelength ⁇ 2.
- the wavelength ⁇ 2 is not particularly limited, and is determined by the type of the photochromic molecule. Preferably, light in the visible region is used.
- the method of irradiating light with wavelength ⁇ 2 in the erasing process is not particularly limited.
- a method using a deuterium lamp, a xenon lamp, a mercury lamp, a halogen lamp, an LED, a laser, or the like can be given.
- the time for irradiating the metal complex with light having a wavelength ⁇ 2 is not particularly limited.
- irradiation may be performed for 1 picosecond or longer.
- Information can be recorded again on the metal complex and the information recording medium from which the recorded information has been erased in the above recording process. That is, it is possible to repeatedly record and erase information on the metal complex and the information recording medium according to the present invention.
- information recording, reproducing, and erasing are repeatedly performed using the metal complex according to the present invention and the light having the wavelengths ⁇ 1, ⁇ 2, and ⁇ 3. Can do.
- the wavelengths ⁇ 1, ⁇ 2, and ⁇ 3 are different wavelengths.
- the present invention includes an information recording / reproducing apparatus including a constituent member for executing the above steps of the information recording / reproducing method according to the present invention.
- the information recording / reproducing apparatus concerning this invention should just be provided with the structural member which can implement said each process,
- the concrete structure is not specifically limited.
- the configuration of the information recording / reproducing apparatus according to the present invention includes a light source unit for performing the recording step; a light source unit, a light receiving unit, a light emission intensity measuring unit, and a light emission intensity calculating unit for performing the reproduction step.
- a configuration including a light source unit for performing the erasing step may be mentioned.
- the metal complex according to the present invention has a function as a code. Therefore, the present invention includes an information identification method using the metal complex according to the present invention. Further, the present invention includes an information identification medium used for the method and an information identification apparatus for performing the method.
- the composition containing the metal complex according to the present invention can be used as an information identification medium. That is, the information identification medium according to the present invention includes the composition described in (II) above.
- the shape and form of the information identification medium are not particularly limited.
- the information identification medium according to the present invention can have, for example, shapes and forms of cards, films, seals, armbands and the like molded from a resin containing the metal complex according to the present invention.
- the image, figure, and character printed or printed using the ink containing the metal complex concerning this invention can be used as said information identification medium.
- Such an ink contains the composition described in (II) above, and can be obtained by dispersing the metal complex according to the present invention in a medium and further adding an additive as necessary.
- the medium used here is not particularly limited as long as it is a medium that is usually used for ink.
- the medium described in (II) above can be preferably used.
- the ink can be used as the information identification medium, particularly the encryption medium, for example as follows.
- the ink is applied or printed on both sides or one side of a substrate such as a label, card, film, or seal.
- the color of the ink applied or printed is not particularly limited.
- coating or printing is not specifically limited, either,
- the method used for manufacture of the information recording medium as described in said (II) can be used suitably.
- the method by an inkjet can also be used suitably.
- the applied or printed ink is irradiated with light of wavelength ⁇ 1 to change the structure of the photochromic molecule in the metal complex from a ring-opened body to a ring-closed body.
- encryption information can be written (recorded) in the photochromic molecule.
- the encryption information recorded on the photochromic molecule may be erased by irradiating the ink with a wavelength ⁇ 2 to change the structure of the photochromic molecule in the metal complex from a closed ring to an open ring.
- the light having the wavelength ⁇ 3 (excitation light) is irradiated to the ink that has been recorded or erased as described above.
- the recorded or erased information can be read by measuring the light emission intensity, the light emission quantum yield, the light emission lifetime, and the like.
- recording or erasing is performed based on emission intensity, combination of a plurality of emission intensities, emission quantum yield, emission lifetime, emission rate constant calculated from emission quantum yield and emission lifetime, or a combination of two or more of these.
- the read information may be read. Thereby, the reading accuracy can be improved.
- the read light (light having the wavelength ⁇ 3), the write light, and the light to be erased have different wavelengths, so that the recorded or erased information, that is, the encryption information is deteriorated by the read.
- the emission wavelength can be changed from the visible region to the near infrared region.
- the metal ion and the photochromic molecule the reading light, the writing light, and the erasing light can be freely changed, and a stronger encryption can be realized.
- the type of the metal complex included in the information identification medium according to the present invention may be one type or a plurality of types, but preferably a plurality of types. Thereby, discrimination power (security) can be made higher.
- Such an information identification medium according to the present invention can be manufactured by processing the composition according to the present invention as described above.
- the information identification method according to the present invention includes a step of irradiating light having a wavelength ⁇ 1 to a metal complex having a structure in which a photochromic molecule is coordinated to a metal ion (hereinafter, also referred to as “first irradiation step”).
- first irradiation step a step of irradiating light having a wavelength ⁇ 1 to a metal complex having a structure in which a photochromic molecule is coordinated to a metal ion
- a step of irradiating the metal complex with light of wavelength ⁇ 2 (hereinafter also referred to as “second irradiation step”), and a wavelength of the metal complex after the second irradiation step.
- irradiating light of ⁇ 3, receiving light emitted from the metal complex, and measuring the emission intensity of the emitted light (hereinafter also referred to as “second light emission measurement step”), the first light emission measurement step and the first light emission measurement step;
- Work to calculate each luminescence intensity measured in the two luminescence measurement process (Hereinafter also referred to as “calculation step”) and a step of identifying identification information associated with the result obtained in the calculation step (hereinafter also referred to as “identification step”).
- Other specific configurations are not particularly limited.
- V-1 First Irradiation Step
- the metal complex according to the present invention is irradiated with light having a wavelength ⁇ 1, and the structure of the photochromic molecule in the metal complex is changed from a ring-opened body to a ring-closed body. Change.
- the information identification unit containing the metal complex according to the present invention irradiates the focused light of wavelength ⁇ 1 to the information identification unit of the information identification medium.
- the structure of the photochromic molecule of the metal complex according to the present invention is changed.
- the wavelength ⁇ 1 is not particularly limited, and is determined by the type of the photochromic molecule. Preferably, light in the ultraviolet region is used.
- the method of irradiating light with wavelength ⁇ 1 in the first irradiation step is not particularly limited. For example, a method using a deuterium lamp, a xenon lamp, a mercury lamp, a halogen lamp, an LED, a laser, or the like can be given.
- the time for irradiating the metal complex with light having a wavelength ⁇ 1 is not particularly limited.
- irradiation may be performed for 1 picosecond or longer.
- V-2 First Luminescence Measurement Step
- the metal complex or information identification medium after the first irradiation step is irradiated with light of wavelength ⁇ 3 (excitation light).
- the metal complex or the information identification medium emits light.
- the emitted light is received and the intensity of the emitted light is measured.
- the wavelength ⁇ 3 is not particularly limited, and is determined by the type of the metal ion.
- the method of irradiating the light with the wavelength ⁇ 3 in the first light emission measurement step is not particularly limited. For example, a method using a deuterium lamp, a xenon lamp, a mercury lamp, a halogen lamp, an LED, a laser, or the like can be given.
- the time for irradiating the metal complex with light having a wavelength ⁇ 3 is not particularly limited.
- irradiation may be performed for 1 picosecond or longer.
- the intensity of the entire emission may be measured without dispersing the emission from the metal complex, or the intensity of the emission spectrum obtained by separating the emission may be measured. Alternatively, only the intensity of the line spectrum of a specific wavelength of the spectral emission spectrum may be measured.
- the configuration for measuring the intensity of the entire luminescence from the metal complex can simplify the apparatus configuration for measuring the luminescence intensity, and at the same time, the first luminescence measurement step. Can be shortened. If the intensity of the emission spectrum obtained by separating the emitted light is measured, the accuracy of identifying information can be improved. Furthermore, if only the intensity of the line spectrum of the specific wavelength of the spectral emission spectrum is measured, the apparatus configuration for measuring the emission intensity can be simplified, and at the same time, the first emission measurement step is performed. The time required can be shortened, and further, the accuracy of identifying information can be improved.
- the number of wavelengths to be selected is not particularly limited, and may be one or may be two or more.
- the accuracy of identifying information can be further improved. For example, if two wavelengths are selected, the ratio of the intensities of the line spectra of these two wavelengths can be calculated in a calculation process described later, and information can be identified in the identification process described later using the ratio. it can. Therefore, information can be identified with higher accuracy. Further, if two wavelengths are selected, the time required for the first light emission measurement step and the calculation step described later can be shortened. Therefore, the processing time of the information identification method according to the present invention can be shortened.
- the wavelength to be selected may be appropriately selected according to the light emission characteristics of the type of metal complex or information identification medium to be used, and is not particularly limited.
- the wavelength of light emission by magnetic dipole transition or light emission by electric dipole transition can be selected.
- the wavelength of the light emission by the said magnetic dipole transition and the light emission by an electric dipole transition is determined by the kind of metal complex.
- the luminescence quantum yield and the luminescence lifetime may be measured and used in the calculation step, the identification step, or the luminescence quantum yield. And a radiation rate constant calculated from the emission lifetime.
- a combination of two or more of emission intensity, a combination of a plurality of emission intensities, emission quantum yield, emission lifetime, and emission rate constant calculated from the emission quantum yield and emission lifetime can be used in the calculation step and identification step.
- the discriminating power can be improved.
- (V-3) Second irradiation step the metal complex according to the present invention is irradiated with light having a wavelength of ⁇ 2, and the structure of the photochromic molecule in the metal complex is changed from a ring-closed body to a ring-opened body. Change.
- the information identification medium according to the present invention described above the information identification unit containing the metal complex according to the present invention is irradiated with the focused light of wavelength ⁇ 2 to be in the information identification unit of the information identification medium.
- the structure of the photochromic molecule of the metal complex according to the present invention is changed.
- the wavelength ⁇ 2 is not particularly limited, and is determined by the type of the photochromic molecule. Preferably, light in the visible region is used.
- the method of irradiating light with wavelength ⁇ 2 in the second irradiation step is not particularly limited.
- a method using a deuterium lamp, a xenon lamp, a mercury lamp, a halogen lamp, an LED, a laser, or the like can be given.
- the time for irradiating the metal complex with light of wavelength ⁇ 2 is not particularly limited.
- irradiation may be performed for 1 picosecond or longer.
- V-4 Second luminescence measurement step
- the second luminescence measurement step is performed except that the metal complex or information identification medium after the second irradiation step is irradiated with light (excitation light) having a wavelength ⁇ 3. This is the same as the first luminescence measurement step. Therefore, detailed description thereof is omitted here.
- V-5) Calculation Step the light emission intensity measured in the first light emission measurement step and the second light emission measurement step is calculated. For example, when measuring the intensity of the entire light emission from the metal complex in the first light emission measurement step and the second light emission measurement step, the ratio of the light emission intensities of both is calculated.
- first calculation sub-step When measuring the intensity
- the ratio between the ratio calculated in the first calculation sub-step and the ratio calculated in the second calculation sub-step may be calculated (hereinafter also referred to as “third calculation sub-step”).
- the number of line spectra to be selected is not particularly limited, and may be two or three or more. By increasing the number, information identification accuracy can be increased.
- the ratio of the intensity of the corresponding line spectrum is calculated.
- first luminescence measurement step and the second luminescence measurement step when measuring the intensity of the line spectra of a plurality of wavelengths, the ratio of the intensity of the plurality of line spectra measured in the first luminescence measurement step, and The ratios of the intensities of the plurality of line spectra measured in the two-emission measurement process are respectively calculated (“first calculation sub process” and “second calculation sub process”). Further, the ratio of the calculated ratios may be calculated (“third calculation sub-step”).
- the ratio between the two may be calculated as in the case of the luminescence intensity. Or what is necessary is just to calculate ratio of both about the radiation rate constant computed from the light emission quantum yield and the light emission lifetime.
- identification information associated with the ratio calculated in the calculation step is identified. Specifically, identification information associated with the ratio calculated in at least one of the first calculation sub-process, the second calculation sub-process, and the third calculation sub-process may be identified. At this time, considering the identification accuracy, the identification information associated with the ratio calculated in two sub-steps among the first calculation sub-step, the second calculation sub-step, and the third calculation sub-step is identified. Preferably, identification information associated with the ratio is identified in all three sub-steps.
- the identification step Then, what is necessary is just to identify the identification information matched with the ratio.
- the above “identification information associated with the calculated ratio” means the following.
- Each metal complex according to the present invention has unique photochromic reactivity and light emission characteristics. That is, each of the metal complexes according to the present invention exhibits unique responsiveness to the wavelength ⁇ 1, the wavelength ⁇ 2, and the wavelength ⁇ 3. Therefore, the ratio calculated in the above calculation step is a value unique to each metal complex. Therefore, the above ratio can be associated with a metal complex having the ratio.
- the “identification information associated with the calculated ratio” can also refer to a metal complex corresponding to the ratio.
- the identification information includes any information encrypted by such a metal complex.
- the information identification method according to the present invention specifies (identifies) a metal complex or a metal complex contained in an information identification medium using both the photochromic property and the light emission property of the metal complex according to the present invention,
- the identification information associated with the complex is identified and authenticated. Therefore, this is an information identification method having an unprecedented high level of discrimination power (security).
- the light intensity or the light intensity ratio, the emission quantum yield, the emission quantum yield ratio, the emission lifetime, the emission lifetime ratio, the emission rate constant, the emission rate constant ratio, or a combination thereof Therefore, even if the metal complex is deteriorated, it is possible to specify the substance, and there is no restriction on use conditions such as temperature.
- the metal complex since the metal complex is colorless and transparent, it is not visible in a normal state, and has better security. Furthermore, when a single metal ion is used, it is possible to recover a metal ion that is a valuable resource even after use.
- the present invention includes an information identification device including a constituent member for executing the above-described steps of the information identification method according to the present invention.
- the information identification apparatus concerning this invention should just be provided with the structural member which can implement said each process, and the specific structure is not specifically limited.
- the information recording / reproducing apparatus includes a light source unit for performing the first irradiation step; a light source unit for performing the first light emission measurement step, a light receiving unit, a light emission intensity calculation unit; A light source unit for performing an irradiation step; a light source unit for performing a second light emission measurement step, a light receiving unit, a light emission intensity calculation unit; a light emission intensity analysis unit for performing a calculation step; and an identification unit for performing an identification step
- a light source unit for performing the first irradiation step a light source unit for performing the first light emission measurement step, a light receiving unit, a light emission intensity calculation unit
- a light source unit for performing an irradiation step a light source unit for performing a second light emission measurement step, a light receiving unit, a light emission intensity calculation unit
- a light emission intensity analysis unit for performing a calculation step
- an identification unit for performing an identification step
- Example 1 Tris (hexafluoroacetylacetonato) [1,2-bis (2-methyl-1-benzothiophene-1,1-dioxide-3-yl) perfluorocyclopentene] europium (III) (Tris ( hexafluoroacetylacetonato) [1,2-bis (2-methyl-1-benzothiophene-1,1-dioxide-3-yl) perfluorocyclopentene] europium (III), hereinafter referred to as [Eu (BTFO4) (HFA) 3 ] as appropriate.
- 1 H-NMR measurement was performed using a JEOL AL-300 spectrometer (300 MHz), and 1 H-NMR chemical shift was determined using tetramethylsilane (TMS) as an internal standard.
- TMS tetramethylsilane
- the IR measurement was performed using a JASCO FT / IR-420 spectrometer, and the ESI-Mass measurement was performed using a JEOL JMS-700 Mstation.
- Example 2 Luminous properties of [Eu (BTFO4) (HFA) 3 ]] Ring-opening ligand (BTFO4-O) coordinated [Eu (BTFO4) (HFA) 3 ] and ring-closing ligand (BTFO4-C) coordinated [Eu (BTFO4) (HFA) 3 ]
- BTFO4-O Ring-opening ligand
- BTFO4-C ring-closing ligand
- 592 nm - emission (5 D 0 7 F 1) is an emission by a magnetic dipole transition
- a magnetic dipole transition depends on Eu (III) coordination environment (symmetry of the complex) surrounding the ion It is known not to.
- the emission by electric dipole transition 615 nm - emission (5 D 0 7 F 2) varies greatly depending on the symmetry of the complex. Therefore, in order to evaluate the coordination environment of Eu (III) ions, it is possible to use a relative light emission intensity change of the electric dipole transition with respect to a light emission intensity change of the magnetic dipole transition.
- the emission intensity of 592nm The obtained emission spectrum (luminescence due to magnetic dipole transition: 5 D 0 - 7 F 1 ) is normalized to be 1. Normalization result, as shown in FIG. 2, the relative emission intensity of 615nm with the visible light irradiation (emission by electric dipole transition: 5 D 0 - 7 F 2 ) was found to be increased.
- the emission intensity changes very sensitively due to the change in the molecular structure accompanying the photochromic reaction of the ligand.
- [Eu (BTFO4) (HFA) 3 ] does not overlap the emission spectrum and the absorption spectrum when (BTFO4) is a ring-opened body or a ring-closed body, as will be described later. Therefore, the change in emission intensity at 615 nm cannot be considered due to optical switching based on resonance energy transfer. Therefore, in [Eu (BTFO4) (HFA) 3 ], the increase in emission intensity by visible light irradiation is caused by the change in the coordination structure of the complex as a result of the change in the molecular structure of the photochromic molecule by the visible light irradiation. I think that. In addition, the change in coordination structure due to the photochromic reaction is supported by the fact that the maximum wavelength of light emission derived from the electric dipole transition changes before and after the light irradiation.
- Example 3 Photochromic characteristics of [Eu (BTFO4) (HFA) 3 ]] Absorption of [Eu (BTFO4) (HFA) 3 ] coordinated with the ring-opened ligand (BTFO4-O) obtained in Example 1 in an ethyl acetate solution (1.6 ⁇ 10 ⁇ 5 M) The spectrum was measured using JASCO V-550. The obtained absorption spectrum is shown by a solid line in FIG.
- Example 4 Luminescence characteristics when [Eu (BTFO4) (HFA) 3 ] is continuously irradiated with excitation light] Ring-opening ligand (BTFO4-O) coordinated [Eu (BTFO4) (HFA) 3 ] and ring-closing ligand (BTFO4-C) coordinated [Eu (BTFO4) (HFA) 3 ] Then, 526 nm excitation light was continuously irradiated, and the change over time in the emission characteristics was measured.
- FIG. 4 shows the temporal change in the emission intensity at 615 nm.
- the emission lifetime is determined by exciting [Eu (BTFO4) (HFA) 3 ] with a Nd-YAG laser (Spectraphysics INDI) at room temperature and detecting the emission with a Photomultiplier (Hamamatsu Photomultiplier R5108). It was measured. The emission spectrum was measured using JASCO FP-6600. For the measurement, an ethyl acetate solution of [Eu (BTFO4) (HFA) 3 ] was used, and the concentration was 1.6 ⁇ 10 ⁇ 5 M.
- the light emission quantum yield ( ⁇ emi ) was obtained from the following equation.
- ⁇ emi ⁇ ref ⁇ ( Aemi / Aemi-r ) ⁇ ( Aabs-r / Aabs ) ⁇ (n ethyl acetate / nacetone ) 2
- each symbol indicates the following numerical value.
- the information and the code recorded in the photochromic molecule can be read out not only by the measurement of the luminescence intensity but also by a simple method such as the luminescence quantum yield measurement and / or the luminescence lifetime measurement.
- Example 6 Tris (hexafluoroacetylacetonato) [1,2-bis (2-methyl-1-benzothiophene-1,1-dioxide-3-yl) perfluorocyclopentene] neodymium (III) (Tris ( hexafluoroacetylacetonato) [1,2-bis (2-methyl-1-benzothiophene-1,1-dioxide-3-yl) perfluorocyclopentene] Neodymium (III), hereinafter referred to as [Nd (BTFO4) (HFA) 3 ] as appropriate. ) By reacting [Nd (HFA) 3 (H 2 O) 2] and BTFO4, was synthesized Nd (III) complex [Nd (BTFO4) (HFA) 3].
- FIG. 10 shows an absorption spectrum of benzene in an acetone solution (3.0 ⁇ 10 ⁇ 3 M).
- the absorption spectrum shown in FIG. 10 is an absorption spectrum derived from the Nd (III) ion of [Nd (BTFO4) (HFA) 3 ].
- the absorption bands derived from (BTFO4-O) and (BTFO4-C) of [Nd (BTFO4) (HFA) 3 ] are not shown in FIG. 10 because they exist on the shorter wavelength side. The same.
- FIG. 10 shows an absorption spectrum of benzene in an acetone solution (3.0 ⁇ 10 ⁇ 3 M).
- the absorption spectrum shown in FIG. 10 is an absorption spectrum derived from the Nd (III) ion of [Nd (BTFO4) (HFA) 3 ].
- the absorption bands derived from (BTFO4-O) and (BTFO4-C) of [Nd (BTFO4) (HFA) 3 ] are not shown in FIG. 10 because they
- the solid line is the absorption spectrum of [Nd (BTFO4) (HFA) 3 ] coordinated by the ring-opened ligand (BTFO4-O), and the dotted line is a ring-closed product that is a colored product after light irradiation. It is an absorption spectrum of [Nd (BTFO4) (HFA) 3 ] coordinated by a ligand (BTFO4-C).
- the metal complex according to the present invention has the above-described configuration, and has a characteristic that the emission intensity of the metal ion due to the structural change of the ligand, particularly the emission intensity and the emission intensity change are significantly large.
- the metal complex according to the present invention is different in the absorption band (writing, erasing) based on the photochromic molecule from the absorption band of the metal complex, that is, the wavelength of excitation light (reading) and the emission wavelength of the metal complex (memory detection). It is possible to read the optically recorded information without destroying it.
- the metal complex according to the present invention can be used as an information recording medium, a nonvolatile memory, and a switching element. Furthermore, this photochromic molecule has the characteristic that optical information can be recorded in units of one molecule. Therefore, the metal complex according to the present invention is very useful as a new material that supports the information society.
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Abstract
Description
当該フォトクロミック分子は、各反応点炭素にそれぞれ直接結合する2つの基を介して金属イオンに配位しており、当該基は、それぞれ独立して下記式群(1)
R1およびR2はそれぞれ独立して、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、または、置換若しくは無置換のアリール基を示し、
R3およびR4はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R3とR4とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成し、
環Aは基X、基Xと結合する反応点炭素および該反応点炭素に隣接する炭素原子と共に形成された炭化水素環または複素環を示し、当該炭化水素環または複素環は単環であるか、またはさらに1以上の炭化水素環または複素環と縮合環を形成し、
環Bは基Y、基Yと結合する反応点炭素および該反応点炭素に隣接する炭素原子と共に形成された炭化水素環または複素環を示し、当該炭化水素環または複素環は単環であるか、またはさらに1以上の炭化水素環または複素環と縮合環を形成している。)
で表される構造を有する配位子であることを特徴とする〔1〕に記載の金属錯体。
R1およびR2はそれぞれ独立して、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、または、置換若しくは無置換のアリール基を示し、
R3およびR4はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R3とR4とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成し、
DおよびEはそれぞれ独立して炭素原子または窒素原子を示し、
R5およびR6はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R5とR6とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成し、
R7およびR8はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R7とR8とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成する。)
または、下記一般式(4)
R1およびR2はそれぞれ独立して、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、または、置換若しくは無置換のアリール基を示し、
R3およびR4はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R3とR4とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成し、
TおよびUはそれぞれ独立して炭素原子または硫黄原子を示し、
R9およびR10はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基である。)
で表される構造を有する配位子であることを特徴とする〔1〕または〔2〕に記載の金属錯体。
R3およびR4はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R3とR4とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成している。)
で表される構造を有する配位子であることを特徴とする〔1〕~〔3〕のいずれかに記載の金属錯体。
から選択されるいずれかの構造を有する配位子が、上記金属イオンに対して、さらに配位していることを特徴とする〔1〕~〔4〕のいずれかに記載の金属錯体。
R3およびR4はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R3とR4とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成し、
R11およびR12はそれぞれ独立して、炭素数1~8のアルキル基、炭素数1~8のフッ素置換アルキル基、またはフェニル基を示し、
Mは金属イオンを示し、nは1~5の整数を示し、mは0~4の整数を示し、nとmとの和は6以下である。)
で表される構造を有することを特徴とする金属錯体。
配位子の分子構造の変化による金属錯体の発光特性変化を大きくするという上記課題を解決するためには、当該分子構造の変化を大きくすればよいと考えられる。当該分野の技術常識に基づけば、配位子の分子構造の変化を大きくするためにはフォトクロミック反応の反応中心(ジアリールエテン系では閉環/開環反応に関与する2つの反応点炭素)近傍の分子構造が大きく変化するようなフォトクロミック分子を用いることが重要であると考えられる。
上記フォトクロミック分子としては、ジアリールエテン系のフォトクロミック分子であって、各反応点炭素にそれぞれ直接結合する2つの上記式群(1)から選択されるいずれかの基を介して金属イオンに配位可能なフォトクロミック分子であれば特に限定されるものではないが、例えば、下記一般式(2)
本発明にかかる金属錯体で用いられる上記金属イオンは、特に限定されるものではなく、例えば、元素周期表の1A族(Li,Na,K,Rb,Cs,Fr)、2A族(Be,Mg,Ca,Sr,Ba,Ra)、3A族(Sc,Y)、4A族(Ti,Zr,Hf)、5A族(V,Nb,Ta)、6A族(Cr,Mo,W)、7A族(Mn,Tc,Re)、8族(Fe,Ru,Os,Co,Rh,Ir,Ni,Pd,Pt)、1B族(Cu,Ag,Au)、2B族(Zn,Cd,Hg)、3B族(Al)、およびランタノイド系列(La,Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu)、アクチノイド系列(Ac,Th,Pa,U,Np,Pu,Am,Cm,Bk,Cf,Es,Fm,Md,No,Lr)の金属のイオンが挙げられる。すなわち、どのような金属のイオンであっても、上記ジアリールエテン系のフォトクロミック分子を配位させると、フォトクロミック分子の分子構造の変化による金属イオンの発光特性の変化が大きい金属錯体を得ることができる。
本発明にかかる金属錯体においては、上記金属イオンに対して、上記フォトクロミック分子以外の配位子が配位していてもよい。そのような配位子としては、具体的には、ピリジンおよびその誘導体;ピリジン以外の窒素含有複素環およびその誘導体;エチレンジアミン、ニトロ、シアノおよびその誘導体;ケトンおよびその誘導体;スルホニルおよびその誘導体;チオ化合物およびその誘導体;並びにホスフィンオキシドおよびその誘導体を挙げることができる。
<本発明にかかる金属錯体の発光特性>
本発明にかかる金属錯体に、その金属イオンに特定の波長λ3の光を照射すると、当該金属イオンが励起され発光する。このとき、上記フォトクロミック分子の分子構造、換言すればフォトクロミック分子が開環体であるのか、もしくは閉環体であるのかによって、上記金属イオンの発光特性が異なる。すなわち、本発明にかかる金属錯体では、波長λ1の光を照射した後と、波長λ2の光を照射した後とで、波長λ3の光を用いて励起した時の上記金属イオンの発光特性が異なる。
本発明にかかる金属錯体のフォトクロミック分子は、波長λ1および波長λ2の光の照射によって異なる分子構造に変化する。この分子構造の変化によりフォトクロミック分子は異なる波長に吸収バンドを持つようになる。本発明の金属錯体について、波長λ1および波長λ2の光の照射によって、フォトクロミック分子の分子構造を可逆的に変化させたときの吸収スペクトルを測定したところ、異なる分子構造を有する金属錯体のいずれもが、金属イオンの励起光の波長より低波長に吸収バンドを有するという予期せぬ結果が得られた。
本発明にかかる金属錯体は、以下のような性能を有する。
本発明にかかる組成物は、上述した本発明にかかる金属錯体と、媒体とを含有する組成物である。上記組成物には、上述した本発明にかかる金属錯体を1種類単独で含有させてもよいし、複数種類の金属錯体を混合して含有させてもよい。本発明にかかる組成物において、本発明にかかる金属錯体の含有量は、特に限定されるものではなく、用途や上記媒体の種類に応じて適宜設定されるものである。
本発明にかかる金属錯体は、光によって光を高速に増幅させることが可能である。したがって、本発明には、本発明にかかる金属錯体を用いた光強度調節方法も含まれる。さらに、本発明には、該方法に用いる光スイッチや、該光スイッチを備える光増幅装置も含まれる。
本発明にかかる金属錯体は、上述したように、情報を記録再生する用途に好適に用いることができる。したがって、本発明には、本発明にかかる金属錯体を用いた情報記録再生方法も含まれる。さらに、本発明には、該方法に用いる情報記録媒体や分子メモリ、該方法を実施する情報記録再生装置も含まれる。
上記記録工程では、本発明にかかる金属錯体に、波長λ1の光を照射して、該金属錯体中のフォトクロミック分子の構造を開環体から閉環体に変化させる。この構造変化を利用することにより、上記フォトクロミック分子に情報を記録することができる。上記の本発明にかかる情報記録媒体に情報を記録する場合、記録層に対して集束した波長λ1の光を照射することによって、該情報記録媒体の照射部分にある本発明にかかる金属錯体のフォトクロミック分子の構造を変化させ、情報を記録する。
上記再生工程では、本発明にかかる金属錯体に、波長λ3の光を照射して、該金属錯体を発光させる。そして、この発光の発光強度を測定し、その発光強度に基づき、上記記録工程において上記フォトクロミック分子に記録された情報を再生する。より詳しく説明すると、上記再生工程では、まず、上記記録工程で情報が記録された上記金属錯体に、波長λ3の光を照射する。これにより、該金属錯体は励起され、発光する。次に、上記再生工程では、該発光の発光強度を測定する。そして、測定した発光強度に基づき、上記金属錯体のフォトクロミック分子が、開環体であるのか、もしくは、閉環体であるのかを判別する。これにより、該金属錯体に記録された情報を再生する。
上記消去工程では、本発明にかかる金属錯体に、波長λ2の光を照射して、該金属錯体中のフォトクロミック分子の構造を閉環体から開環体に変化させる。このように、上記フォトクロミック分子の構造を変化させることにより、上記フォトクロミック分子に記録された情報を消去することができる。本発明にかかる情報記録媒体に記録された情報を消去する場合、記録層の全体に対して、波長λ2の光を照射することによって消去することができる。
本発明にかかる金属錯体は、上述したように、暗号としての機能を有するものである。したがって、本発明には、本発明にかかる金属錯体を用いた情報識別方法も含まれる。さらに、本発明には、該方法に用いる情報識別媒体や、該方法を実施する情報識別装置も含まれる。
上記第1照射工程では、本発明にかかる金属錯体に、波長λ1の光を照射して、該金属錯体中のフォトクロミック分子の構造を開環体から閉環体に変化させる。上記の本発明にかかる情報識別媒体を用いる場合、本発明にかかる金属錯体を含有する情報識別部に対して集束した波長λ1の光を照射することによって、該情報識別媒体の情報識別部にある本発明にかかる金属錯体のフォトクロミック分子の構造を変化させる。
上記第1発光測定工程では、まず、上記第1照射工程後の金属錯体または情報識別媒体に対して波長λ3の光(励起光)を照射する。これにより、該金属錯体または情報識別媒体は発光する。次に、この発光を受光すると共に、発光の強度を測定する。
上記第2照射工程では、本発明にかかる金属錯体に、波長λ2の光を照射して、該金属錯体中のフォトクロミック分子の構造を閉環体から開環体に変化させる。上記の本発明にかかる情報識別媒体を用いる場合、本発明にかかる金属錯体を含有する情報識別部に対して集束した波長λ2の光を照射することによって、該情報識別媒体の情報識別部にある本発明にかかる金属錯体のフォトクロミック分子の構造を変化させる。
上記第2発光測定工程は、上記第2照射工程後の金属錯体または情報識別媒体に対して波長λ3の光(励起光)を照射することを除いて、上記第1発光測定工程と同一である。そのため、ここでは、その詳細な説明は省略する。
上記演算工程では、上記第1発光測定工程および第2発光測定工程で測定した発光強度を演算する。例えば、上記第1発光測定工程および第2発光測定工程で上記金属錯体からの発光全体の強度を測定する場合、両者の発光強度の比を演算する。
上記識別工程では、上記演算工程において演算された比に対応付けられた識別情報を識別する。具体的には、上記第1演算サブ工程、第2演算サブ工程、および第3演算サブ工程のうち、少なくとも1つのサブ工程で演算された比に対応付けられた識別情報を識別すればよい。このとき、識別精度を考慮すると、上記第1演算サブ工程、第2演算サブ工程、および第3演算サブ工程のうち、2つのサブ工程で演算された比に対応付けられた識別情報を識別することが好ましく、3つ全てのサブ工程で比に対応付けられた識別情報を識別することがさらに好ましい。
[Eu(HFA)3(H2O)2]と1,2-bis(2-methyl-1-benzothiophene-1,1-dioxide-3-yl) perfluorocyclopentene(BTFO4)とを反応させることによって、Eu(III)錯体[Eu(BTFO4)(HFA)3]を合成した。なお、BTFO4は、Jeong, Y. C.; Yang, S. I.; Ahn, K. H.; Kim, E. Chem. Commun. 2005, 2503-2505に記載の方法により合成した。
開環体配位子(BTFO4-O)が配位した[Eu(BTFO4)(HFA)3]および閉環体配位子(BTFO4-C)が配位した[Eu(BTFO4)(HFA)3]の発光特性の比較検討を行った。
実施例1で得られた開環体配位子(BTFO4-O)が配位した[Eu(BTFO4)(HFA)3]の酢酸エチル溶液中(1.6×10-5M)中における吸収スペクトルを、JASCO V-550を用いて測定した。得られた吸収スペクトルを図3に実線で示す。
開環体配位子(BTFO4-O)が配位した[Eu(BTFO4)(HFA)3]および閉環体配位子(BTFO4-C)が配位した[Eu(BTFO4)(HFA)3]に、526nmの励起光を連続照射し、発光特性の経時変化を測定した。図4に615nmの発光強度の時間的変化を示す。なお、図4中、白丸は開環体配位子(BTFO4-O)が配位した[Eu(BTFO4)(HFA)3]の結果を、黒丸は閉環体配位子(BTFO4-C)が配位した[Eu(BTFO4)(HFA)3]の結果を示す。図4に示されるように、励起光を連続照射しても開環体配位子(BTFO4-O)が配位した[Eu(BTFO4)(HFA)3]および閉環体配位子(BTFO4-C)が配位した[Eu(BTFO4)(HFA)3]の発光強度や発光スペクトルは変化しないことが分かった。このことから、[Eu(BTFO4)(HFA)3]はその発光強度変化を526nmの励起光を用いて非破壊的に読み出すことが可能であることが判る。
[Eu(BTFO4)(HFA)3]において観測された発光強度変化についてより詳細な知見を得るために、速度論解析を行った。
Φemi=Φref×(Aemi/Aemi-r)×(Aabs-r/Aabs)×(nethyl acetate/nacetone)2
なお、ここで、各記号は以下の数値を示す。
Φemi=[Eu(BTFO4)(HFA)3]の発光量子収率
Φref=[Eu(HFA)3BIPHEPO]の発光量子収率
Aemi=[Eu(BTFO4)(HFA)3]の発光面積
Aemi-r=[Eu(HFA)3BIPHEPO]の発光面積
Aabs-r=[Eu(HFA)3BIPHEPO]の吸収面積
Aabs=[Eu(BTFO4)(HFA)3]の吸収面積
nethyl acetate=酢酸エチルの屈折率
nacetone=アセトンの屈折率
開環体配位子(BTFO4-O)が配位した[Eu(BTFO4)(HFA)3]および閉環体配位子(BTFO4-C)が配位した[Eu(BTFO4)(HFA)3]の発光量子収率(Φemi)、発光寿命(τemi)および放射速度定数(kr)を表1に示す。
[Nd(HFA)3(H2O)2]とBTFO4とを反応させることによって、Nd(III)錯体[Nd(BTFO4)(HFA)3]を合成した。
Claims (17)
- 上記フォトクロミック分子は、下記一般式(2)
R1およびR2はそれぞれ独立して、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、または、置換若しくは無置換のアリール基を示し、
R3およびR4はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R3とR4とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成し、
環Aは基X、基Xと結合する反応点炭素および該反応点炭素に隣接する炭素原子と共に形成された炭化水素環または複素環を示し、当該炭化水素環または複素環は単環であるか、またはさらに1以上の炭化水素環または複素環と縮合環を形成し、
環Bは基Y、基Yと結合する反応点炭素および該反応点炭素に隣接する炭素原子と共に形成された炭化水素環または複素環を示し、当該炭化水素環または複素環は単環であるか、またはさらに1以上の炭化水素環または複素環と縮合環を形成している。)
で表される構造を有する配位子であることを特徴とする請求項1に記載の金属錯体。 - 上記フォトクロミック分子は、下記一般式(3)
R1およびR2はそれぞれ独立して、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、または、置換若しくは無置換のアリール基を示し、
R3およびR4はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R3とR4とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成し、
DおよびEはそれぞれ独立して炭素原子または窒素原子を示し、
R5およびR6はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R5とR6とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成し、
R7およびR8はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R7とR8とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成する。)
または、下記一般式(4)
R1およびR2はそれぞれ独立して、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、または、置換若しくは無置換のアリール基を示し、
R3およびR4はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R3とR4とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成し、
TおよびUはそれぞれ独立して炭素原子または硫黄原子を示し、
R9およびR10はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基である。)
で表される構造を有する配位子であることを特徴とする請求項1または2に記載の金属錯体。 - 上記フォトクロミック分子は、下記一般式(5)
R3およびR4はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R3とR4とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成している。)
で表される構造を有する配位子であることを特徴とする請求項1~3のいずれか1項に記載の金属錯体。 - 下記一般式(7)
R3およびR4はそれぞれ独立して、水素原子、アルキル基、アルコキシル基、ハロゲン原子、フッ素置換アルキル基、シアノ基、水酸基、カルボキシル基、置換若しくは無置換のアリール基であるか、あるいは、R3とR4とで、置換若しくは無置換の炭化水素環または置換若しくは無置換の複素環を形成し、
R11およびR12はそれぞれ独立して、炭素数1~8のアルキル基、炭素数1~8のフッ素置換アルキル基、またはフェニル基を示し、
Mは金属イオンを示し、nは1~5の整数を示し、mは0~4の整数を示し、nとmとの和は6以下である。)
で表される構造を有することを特徴とする金属錯体。 - 上記金属イオンは、希土類イオンであることを特徴とする請求項1~6のいずれか1項に記載の金属錯体。
- 上記希土類イオンは、3価のイオンであることを特徴とする請求項7に記載の金属錯体。
- 上記3価のイオンは、Ce3+、Nd3+、Sm3+、Eu3+、Tb3+、Dy3+、Er3+、Pr3+、Tm3+またはYb3+であることを特徴とする請求項8に記載の金属錯体。
- 請求項1~9のいずれか1項に記載の金属錯体と、媒体とを含有する組成物。
- 請求項9に記載の組成物を含むことを特徴とする情報識別媒体。
- 請求項1~9のいずれか1項に記載の金属錯体、または請求項10に記載の組成物に対して波長λ1の光を照射することによって、上記フォトクロミック分子に情報を記録する記録工程と、
上記金属錯体または組成物に波長λ3の光を照射し、該金属錯体または組成物からの発光を受光し、該発光の発光強度を測定し、測定された該発光の発光強度に基づき、上記フォトクロミック分子に記録された情報を再生する再生工程とを含むことを特徴とする情報記録再生方法。 - 上記金属錯体または組成物に波長λ2の光を照射することによって、上記フォトクロミック分子に記録された情報を消去する消去工程をさらに含むことを特徴とする請求項12に記載の情報記録再生方法。
- 請求項1~9のいずれか1項に記載の金属錯体、または請求項10に記載の組成物に対して、波長λ1の光を照射する第1照射工程と、
上記第1照射工程後の金属錯体または組成物に対して、波長λ3の光を照射し、該金属錯体または組成物からの発光を受光し、該発光の発光スペクトルを測定する第1発光測定工程と、
上記金属錯体または組成物に対して、波長λ2の光を照射する第2照射工程と、
上記第2照射工程後の金属錯体または組成物に対して、波長λ3の光を照射し、該金属錯体または組成物からの発光を受光し、該発光の発光スペクトルを測定する第2発光測定工程と、
上記第1発光測定工程および第2発光測定工程で測定されたそれぞれの発光スペクトルの強度を演算する演算工程と、
上記演算工程で得られた結果に対応付けられた識別情報を識別する識別工程とを含むことを特徴とする情報識別方法。 - 上記演算工程が、
上記第1発光測定工程で測定された発光スペクトルのうち、複数の特定の波長の線スペクトルの強度の比を演算する第1演算サブ工程と、
上記第2発光測定工程で測定された発光スペクトルのうち、上記複数の特定の波長の線スペクトルの強度を比を演算する第2演算サブ工程とを含み、
上記識別工程では、
上記第1演算サブ工程で演算された比に対応付けられた識別情報を識別し、
さらに、上記第2演算サブ工程で演算された比に対応付けられた識別情報を識別することを特徴とする請求項14に記載の情報識別方法。 - 上記演算工程が、
上記第1発光測定工程で測定された発光スペクトルのうち、複数の特定の波長の線スペクトルの強度の比を演算する第1演算サブ工程と、
上記第2発光測定工程で測定された発光スペクトルのうち、上記複数の特定の波長の線スペクトルの強度を比を演算する第2演算サブ工程と、
上記第1演算サブ工程で演算された比と上記第2演算サブ工程で演算された比との比を演算する第3演算サブ工程とを含み、
上記識別工程では、
上記第3演算サブ工程で演算された比に対応付けられた識別情報を識別することを特徴とする請求項15に記載の情報識別方法。 - 請求項1~9のいずれか1項に記載の金属錯体、または請求項10に記載の組成物を波長λ3の光を用いて励起したときに、該金属錯体または組成物から発せられる発光の発光強度を、波長λ1および波長λ2の光を用いて制御することを特徴とする光強度調節方法。
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US8674116B2 (en) | 2014-03-18 |
JPWO2010134524A1 (ja) | 2012-11-12 |
US20120063289A1 (en) | 2012-03-15 |
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