JP4817309B2 - A light emitting material comprising a tripod type metal complex and a resin composition containing the light emitting material. - Google Patents

Description

  The present invention relates to a light emitting material comprising a rare earth metal complex and a resin composition using the light emitting material, and in particular, although the organic ligand of the metal complex is the same, the type of the central metal ion is changed. The present invention relates to a light emitting material capable of emitting various fluorescent colors including three primary colors of light and a resin composition containing the same.

Conventionally, certain rare earth metal complexes are known as various light emitting materials.
For example, Patent Document 1 describes the use of a rare earth europium complex as a light emitting material in a red light emitting organic EL element, and Patent Documents 2 and 3 describe rare earths that generate fluorescence when irradiated with light. Complexes are described.

Such rare earth metal complexes that generate fluorescence when irradiated with light are expected to be used in various fields.
For example, in the printing field, printed materials that are required to prevent counterfeiting or copying, such as securities such as vouchers and prepaid cards, or documents that must be kept confidential, cannot be viewed with the naked eye under normal visible light. Although it is difficult to visually recognize, phosphor printing ink is used for so-called hidden printing, which emits fluorescence in the visible region by irradiating ultraviolet rays or infrared rays, and prints an image that can be detected by visual observation. In recent years, it has been proposed to use a rare earth metal complex for the phosphor printing ink. Compared with conventional inks using inorganic phosphors, this rare earth metal complex ink is less susceptible to light scattering at the ink formation site, and the presence of ink when the printed matter is viewed under visible light. Can be solved to some extent, and is less likely to cause association in the ink binder and less likely to cause changes in emission intensity due to operating temperature, etc., compared to inks using organic phosphors. have. However, the conventional rare earth metal complex has problems such as low emission intensity and easy crystallization in a binder. In Patent Document 4, as a solution to such a problem, a ligand of a specific phosphorus compound, Europium complexes or terbium complexes having a β-diketone ligand have been proposed.

  Moreover, although the resin sheet which has fluorescence ability is used with forms, such as a light-guide plate of a display, a wavelength change board, an agricultural film, and an ultraviolet cut film, patent document 5 has a hyperbranched structure as a resin sheet. A fluorescent resin sheet in which a rare earth metal complex containing a ligand as a constituent component is dispersed in a resin matrix is described.

  Furthermore, in the field of qualitatively or quantitatively measuring an analyte in a biological sample, a measurement method using a fluorescent substance as a labeling agent is used. This measurement method is a method using a phenomenon in which a certain compound emits a specific emitted light based on an electron level of the compound by irradiation with a certain excitation light. In recent years, rare earth metal complexes that generate fluorescence have been used for this labeling agent (Patent Documents 6 and 7). In particular, Patent Document 7 has a drawback that the stability of conventional β-diketone / rare earth metal ion complexes is low. For the purpose of eliminating the disadvantage that the emission intensity of the conventional EDTA / rare earth metal ion complex is small, by introducing a β-diketone group into the molecule of the EDTA-like compound, it is very stable with the rare earth metal in an aqueous solution. Coordination compounds that form complex complexes and emit extremely high emission intensity are synthesized.

  Furthermore, white light-emitting diodes (LEDs) are attracting attention as next-generation lighting devices that replace fluorescent lamps, and phosphors are also used in the field of white LEDs. That is, as a conventional white LED that emits white light, a combination of a blue LED and a yellow fluorescent material is common, but since red is weak, an ideal white color cannot be produced. As a method for solving this, a combination of an ultraviolet LED and a phosphor material showing three primary colors of red, blue, and green emits white, but there is a problem that the spectral intensity in the red region is small, Development of red phosphors that can be excited efficiently by near-ultraviolet light and blue light, which are the emission center wavelengths of LED chips, has been actively conducted.

  For example, in Non-patent Document 1, Patent Document 8, Patent Document 9, and the like, two types of ligands, ie, a ligand composed of β-diketone and another different ligand were used as the organic ligand. New europium complexes have been proposed. However, since the light emission of such a rare earth metal complex does not provide sufficient characteristics other than red, white is realized in combination with an inorganic phosphor other than red. In addition, even if a phosphor of a rare earth metal complex other than red, which has no problem in terms of emission intensity, has been developed, the phosphor materials of red, blue, and green are different for the reasons described below. There remains a problem that a difference occurs in the deterioration speed and a change in the white hue.

The ligands of rare earth metal complexes include monodentate ligands that have only one coordination site and multidentate ligands that have two or more, and various metal complexes have been reported. Is known to form more stable complexes with multidentate ligands than with monodentate ligands. However, even if the same multidentate ligand is used, the stability constant varies depending on the size and charge density of the rare earth metal ions, so the stability of the metal complex is controlled by the combination of the central metal and the polydentate ligand Is possible.
For example, certain cyclic compounds have been utilized for the extraction of rare earth elements using this property of rare earth metal complexes. That is, for example, in a lanthanoid from La to Lu, the ion size decreases as the atomic number increases, so the selectivity for a specific rare earth that matches the core size of the cyclic organic ligand increases and is extracted more. It makes use of what becomes easier.

  As described above, since the optimum organic ligand is determined by the ionic radius of the central metal of the rare earth metal complex, the rare earth metal complex having various ionic radii can be manufactured using the same organic ligand. Even if the ionic radius of the metal increases, there is a difference between the ionic radius and the core size of the organic ligand. There was a problem of changing.

  In addition, in the rare earth metal complex using two types of ligands, a ligand consisting of β-diketone described in Patent Documents 1, 8, 9 and Non-Patent Document 1, and other different ligands, Since the central metal and the ligand are not one-to-one, there has been a problem with the stability of the complex, particularly the thermal stability.

On the other hand, as a method for selectively separating only a rare earth from a mixture of rare earth such as yttrium and europium and zinc, the present inventors added tris (2-aminoethyl) amine to a solution in which the rare earth and zinc coexist. Furthermore, it has been found that a rare earth metal complex can be formed by adding a specific aldehyde and reacting to precipitate it as a crystal, and by separating it from the solution, only the rare earth can be selectively separated. . (See Patent Document 10)
The present inventors conducted further research focusing on the rare earth metal complex. As a result, the rare earth metal complex was not limited to yttrium and europium, but various ionic radii with the same organic ligand. It is found that a complex with a central metal and a ligand can be prepared for a rare earth metal ion, and that it is based on a tripod structure peculiar to a complex having a specific organic ligand. Discovered and already reported in Non-Patent Document 2.
JP 11-329739 A Japanese Patent Laid-Open No. 11-246510 Japanese Patent Laid-Open No. 2003-81986 JP 2006-77191 A JP 11-323324 A JP 2001-356128 A Japanese Patent Laid-Open No. 7-10819 JP 2003-163376 A JP 2006-73748 A JP 2001-151743 A H. Iwanaga et al., J. Alloys Comp., 408-412, 921 (2006) S. Mizukami, M. Kanesatoet al., Chem. Eur. J., 2003, 9, No. 7, 1521-1528

  The present invention has been made in view of the circumstances as described above, and can generate fluorescence by irradiation of excitation light in a solid or a solution, and the formed complex has high stability, and the resin. It is an object of the present invention to provide a light emitting material that can be formed into various shapes by allowing the mixture to be mixed into the liquid crystal. Another object of the present invention is to provide a rare earth metal-based light emitting material that can form complexes of various metal ions with the same ligand.

As a result of intensive studies to achieve the above-mentioned object, the inventors have found that the tripod complex found by the inventors can be solid or irradiated in solution by irradiating excitation light. The present inventors have found that a light emitting material capable of generating excellent fluorescence and that the tripod complex has excellent thermal stability.
The present invention has been completed based on these findings, and is as follows.
(1) The following general formula (I)

(Wherein, M represents yttrium beam, R ₁ and R ₂ are hydrogen atoms, at least one member selected alkyl group which may have a branch having 1 to 4 carbon atoms, and from the group consisting of halogen atoms Represents one.)
Or the following general formula (II)

(Wherein, M represents yttrium beam, R ₁ and R _2, at least one also selected from an alkyl group, and the group consisting of a halogen atom, a hydrogen atom, have a branch having 1 to 4 carbon atoms Represents.)
A light-emitting material comprising a rare earth complex represented by the formula:
(2) The following general formula (I)

(In the formula, M represents at least one metal selected from yttrium and a lanthanoid , R ₁ and R ₂ represent a hydrogen atom, an alkyl group optionally having 1 to 4 carbon atoms, and a halogen atom. Represents at least one selected from the group consisting of atoms.)
Or the following general formula (II)

(In the formula, M represents at least one metal selected from yttrium and a lanthanoid , R ₁ and R ₂ represent a hydrogen atom, an alkyl group optionally having 1 to 4 carbon atoms, and a halogen atom. Represents at least one selected from the group consisting of atoms.)
A luminescent material comprising a rare earth metal complex represented by the formula:
(3) A resin composition comprising the light emitting material according to (1) or (2) as a light emitting material contained in the resin.
(4) As the luminescent material contained in the resin, the blue luminescent material described in (1), and the red luminescent material in which M in the general formula (I) or the general formula (II) is europium or samarium; And a green light emitting material in which the M in the general formula (I) or the general formula (II) is terbium.
(4) The resin composition according to (3) or (4), wherein the resin is an olefin resin.

  The light-emitting material of the present invention has a very high stability of the rare earth metal complex that is an active ingredient thereof, a high compatibility with an organic solvent, and a very good dispersibility in a resin. In addition to providing a transparent resin composition, the resin has sufficient light-emitting properties. In particular, when the luminescent material of the present invention is used for a white LED, the same organic configuration is used, and different metals are used as the central metal, for example, yttrium for blue, europium or samarium for red, and terbium for green. By using these in combination, it is possible to obtain a good white LED that does not cause the problem of a change in white hue due to a different deterioration rate for each color.

  The luminescent material of the present invention has the following general formula (I)

(In the formula, M represents at least one metal selected from the group consisting of yttrium and lanthanoid, R ₁ and R ₂ are a hydrogen atom, an alkyl group optionally having 1 to 4 carbon atoms, and Represents at least one selected from the group consisting of halogen atoms.)
Or the following general formula (II)

(In the formula, M represents at least one metal selected from the group consisting of yttrium and lanthanoid, R ₁ and R ₂ are a hydrogen atom, an alkyl group optionally having 1 to 4 carbon atoms, and Represents at least one selected from the group consisting of halogen atoms.)
The active ingredient is a rare earth complex represented by the formula:

Specific examples of the general formula (I) include the following compounds ML1 to ML7. Here, for example, the compound described as “ML1” represents a rare earth complex in which R ₁ and R ₂ are each H in the above general formula (I), and when “YL1” is described , M represents a rare earth complex of “Y”.
ML1 (R ₁ = H, R ₂ = H)
ML2 (R ₁ = Me, R ₂ = H)
_{ML3 (R 1 = t-Bu} , R 2 = H)
ML4 (R ₁ = H, R ₂ = t-Bu)
_{ML5 (R 1 = t-Bu} , R 2 = t-Bu)
ML6 (R ₁ = H, R ₂ = Cl)
ML7 (R ₁ = H, R ₂ = Br)

Similarly, specific examples of the general formula (II) include the following compounds ML8 to ML14 shown below in which R ₁ and R ₂ in the general formula (II) are in parentheses, respectively.
ML8 (R ₁ = H, R ₂ = H)
ML9 (R ₁ = Me, R ₂ = H)
_{ML10 (R 1 = t-Bu} , R 2 = H)
ML11 (R ₁ = H, R ₂ = t-Bu)
_{ML12 (R 1 = t-Bu} , R 2 = t-Bu)
ML13 (R ₁ = H, R ₂ = Cl)
ML14 (R ₁ = H, R ₂ = Br)

In the general formula (I) or the general formula (II), M represents a central metal in the complex, and represents at least one metal selected from the group consisting of yttrium and lanthanoid.
Specifically, when M is yttrium, a blue light emitting material emitting fluorescence with a wavelength of 427-472 nm is obtained, and when M is samarium, red light emitting emitting fluorescence with a wavelength of 655-656 nm is obtained. Material was obtained. In the case of europium, a red light emitting material emitting fluorescence with a wavelength of 609-610 nm is obtained, and in the case of terbium, a green light emitting material emitting fluorescence with a wavelength of 547-550 nm is obtained.

Examples of ML1 (M = Y, Sm, Eu, Tb) are shown in FIGS. 1 and 2 for the solid fluorescence spectrum obtained for each metal.
YL1, SmL1, EuL1 and TbL1 were obtained in the following Example 1, Example 6, Example 12 and Example 13, respectively, and the excitation wavelengths were “330 nm”, “398 nm”, “402 nm” and “393 nm” were set.

As is clear from the general formula, the rare earth metal complex represented by the general formula (I) or the general formula (II) in the present invention has a one-to-one ratio between the central metal and the ligand. Compared to rare earth metal complexes using two types of ligands as described in 4, 9, 10 and the like, it is extremely stable.
For example, a commercially available europium complex having a metal ion to ligand ratio of 1: 4 (tris (1,3-diphenyl-1,3-propanedionato)-(1,10-phenanthroline) europium (III)) Melts below 200 ° C., whereas EuL1 exists stably up to 330 ° C. The results of the thermogravimetry (TG) and differential thermal analysis (DTA) of EuL1 are shown in FIG. As is apparent from FIG. 3, no change was observed up to 330 ° C. The results of thermogravimetry (TG) and differential thermal analysis (DTA) of YL1 and TbL1 are shown in FIGS. 4 and 5, respectively. As is apparent from these figures, no change was observed up to 350 ° C. On the other hand, in thermogravimetry (TG) and differential thermal analysis (DTA) of a ligand (H ₃ L1) that does not contain a metal ion, an endothermic peak accompanying melting is observed at 93 ° C. From the results, a decrease in weight due to decomposition was observed. From the above results, it was suggested that a metal complex having a metal ion to ligand ratio of 1: 1 has higher thermal stability than a metal complex or ligand of 1: 4.

In order to investigate the thermal stability of the rare earth metal complex represented by the above general formula (I) or (II) of the present invention, the solid of YL1, TbL1, EuL1 was put in an oven capable of temperature control for 1 hour, Maintained at 250 ° C. After returning the temperature to room temperature, the fluorescence spectrum of each solid was measured with a fluorescence spectrophotometer. Similarly to the above, the respective excitation wavelengths were 330 nm for YL1, 402 nm for EuL1, and 393 nm for TbL1.
The obtained results are as shown in FIG. 6, and it was confirmed that there was almost no change in the fluorescence characteristics before and after heating as compared with the results of FIGS. 1 and 2.

Next, the case where M is yttrium in the light emitting material having the rare earth complex represented by the above general formula (I) or (II) of the present invention as an active ingredient will be described in detail below.
That is, in the conventional rare earth complex-based phosphor, when the central metal is yttrium, unlike the europium complex or the terbium complex, the fluorescence specific to the central metal based on the transition between ff of 4f electrons cannot be emitted. In the metal complex represented by the general formula (I) or (II) of the present invention, the complex in which the central metal M is yttrium may be solid as shown in Examples 1 to 5 in the subsequent stage. Even a liquid obtained by dissolving it in an organic solution similarly emits blue fluorescence.

The rare earth complex represented by the above general formula (I) or (II) of the present invention is produced by a method described later, and as a result, it can be obtained as a yellow powder or a yellow crystal. When both yttrium and other, for example, samarium, europium, or terbium are contained at the same time, the crystals obtained do not show blue fluorescence due to yttrium, as shown in Examples 15 and 16 below. Only red fluorescence by europium or green fluorescence by terbium is shown. That is, when yttrium and other metals coexist, it is clear that yttrium has a kind of sensitizer effect. Yttrium can be obtained at a lower cost than lanthanoid metals, so when manufacturing red phosphors using europium as rare earth metals and green phosphors using terbium, some of them are replaced with cheap yttrium. This has the effect of being inexpensively manufactured.
It was also found that when the crystals thus produced were dissolved in a solvent to form a solution, both fluorescences were shown.

In the above formula, R ₁ and R ₂ are substituents in the organic ligand, and the solubility in an organic solvent varies depending on the types of R ₁ and R ₂ . Therefore, it is possible to control the solubility in an organic solvent by changing the types of R ₁ and R ₂ . This can also be applied to the production of a resin composition, and the dispersibility of the resin used can be controlled by changing the type of substituent R. Actually, as a result of examining the solubility of SmL1 (R ₁ and R ₂ are both H) in an organic solvent, it is soluble in polar solvents such as acetonitrile and methanol, but in hexane which is a nonpolar solvent. It turns out that it doesn't melt at all. On the other hand, when the solubility of SmL5 (having 6 t-Bu groups as R ₁ and R ₂ ) in an organic solvent was examined, a saturated solution at 25 ° C. with respect to hexane as a nonpolar solvent It was found that the concentration of was reached to 7.07 × 10 ⁻⁴ mol · dm ⁻³ .
From the above results, it is clear that the solubility in organic solvents can be controlled by changing the types of R ₁ and R ₂ .

  The tripodal complex represented by the general formula (I) or (II) is produced by the following method A or B in the scheme shown below.

  Since the tripod complex represented by the general formula (I) or (II) has the organic ligand as described above, it has high solubility in an organic solvent and good dispersibility in a resin. Therefore, a resin composition containing a phosphor containing the tripod complex of the present invention as an active ingredient has high transparency and good optical properties.

  Examples of the resin used in the resin composition of the present invention include olefin resin, acrylic resin, polycarbonate resin, epoxy resin, polystyrene resin, polyethylene resin, polypropylene resin, silicon resin, fluorine resin, ABS resin, and urethane resin. Among these, olefin resins are particularly preferable from the viewpoint of processability.

  Fluorescence characteristics were examined using a resin composition containing a tripod complex represented by the general formula (I) or (II). YL1, TbL1, and EuL1 were each kneaded with commercially available low density polyethylene to prepare a resin composition, and a sheet-like resin molded body was obtained. The fluorescence spectrum of the obtained sheet-shaped resin molding was measured with a fluorescence spectrophotometer. The excitation wavelength was 330 nm for YL1, 393 nm for TbL1, and 402 nm for EuL1, as in FIGS. The results are as shown in FIG. 7, and it was found that the fluorescence characteristics of the rare earth complex are reflected in the sheet-like resin molded body as compared with the results of FIGS.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
Example 1
<Synthesis of YL1 and its fluorescence characteristics>
25 mL of methyl alcohol was added to 1.0 mmol of yttrium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Y), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added and heated and stirred at 50-60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of salicylaldehyde was added, and the mixture was heated and stirred at 50-60 ° C. for 2 minutes. During this time, a yellow precipitate was deposited. The solution was allowed to stand for 2 hours, and then the precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.47 g, and the yield was 86%. Elemental analysis values for C ₂₇ H ₂₇ N ₄ O ₃ Y = 544.43, C, 59.37% (calculated value 59.56%), H, 4.94% (calculated value 5.00%), N, 10.11% (calculated value 10.29) %). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1631 cm ^-1 . When the yellow powder was dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to YL1 + Na ⁺ was observed at 567 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, blue fluorescence was observed. In addition, blue fluorescence was also observed in the acetonitrile solution when irradiated with light at 365 nm. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 433 nm was obtained by excitation at 330 nm. As a result of measuring the fluorescence spectrum of the solid yellow powder with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 427 nm was obtained by excitation at 330 nm.

(Example 2)
<Synthesis of YL3 and its fluorescence characteristics>
25 mL of methyl alcohol was added to 1.0 mmol of yttrium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Y), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added and heated and stirred at 50-60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of 3-t-butylsalicylaldehyde was added, and the mixture was heated and stirred at 50-60 ° C. for 5 minutes. This solution was allowed to stand for 13 days. The resulting precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain yellow crystals. The yield was 0.41 g and the yield was 58%. The elemental analysis values are C ₃₉ H ₅₁ N ₄ O ₃ Y = 712.75, C, 65.37% (calculated 65.72%), H, 7.24% (calculated value 7.21%), N, 7.85% (calculated value 7.86%) ) In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1618 cm ^-1 . When yellow crystals were dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to YL3 + H ⁺ was observed at 713 (m / z). When yellow crystals were irradiated with 365 nm light from an ultraviolet lamp, blue fluorescence was observed. In addition, blue fluorescence was also observed in the acetonitrile solution when irradiated with light at 365 nm. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 439 nm was obtained by excitation at 366 nm. As a result of measuring the fluorescence spectrum of the solid yellow crystal with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 445 nm was obtained by excitation at 315 nm.

(Example 3)
<Synthesis of YL4 and its fluorescence characteristics>
To 5.0 mmol of yttrium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Y) is added 40 ml of methyl alcohol, and the mixture is heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 10.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 15.0 mmol of 5-t-butylsalicylaldehyde was added, and the mixture was heated and stirred at 50 to 60 ° C. for 5 minutes. The solution was allowed to stand for 2 days, and then the precipitate was filtered off and washed with cold methanol. Yellow powder was obtained by drying under reduced pressure. The yield was 3.01 g and the yield was 83%. The elemental analysis values are C ₃₉ H ₅₁ N ₄ O ₃ Y0.5H ₂ O = 721.76, C, 65.00% (calculated value 64.90%), H, 7.19% (calculated value 7.26%), N, 7.73 % (Calculated value 7.76%). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1630 cm ^-1 . When the yellow powder was dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to YL4 + Na ⁺ was observed at 735 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, blue fluorescence was observed. In addition, blue fluorescence was also observed in the acetonitrile solution when irradiated with light at 365 nm. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 448 nm was obtained by excitation at 366 nm. As a result of measuring the fluorescence spectrum of the solid yellow powder with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 472 nm was obtained by excitation at 315 nm.

Example 4
<Synthesis of YL6 and its fluorescence characteristics>
25 mL of methyl alcohol was added to 1.0 mmol of yttrium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Y), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 15 ml of a methanol solution containing 3.0 mmol of 5-chlorosalicylaldehyde was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. During this time, a yellow precipitate was deposited. The solution was allowed to stand for 2 hours, and then the precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.48 g and the yield was 74%. Elemental analysis values for C ₂₇ H ₂₄ N ₄ O ₃ Cl ₃ Y = 647.77 are C, 49.92% (calculated value 50.06%), H, 3.62% (calculated value 3.73%), N, 8.42% (calculated) Value 8.65%). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1627 cm ^-1 . When the yellow powder was dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to YL6 + Na ⁺ was observed at 669 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, blue fluorescence was observed. Blue fluorescence was also observed in the acetonitrile solution when irradiated with light at 365 nm. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 442 nm was obtained by excitation at 330 nm. As a result of measuring the fluorescence spectrum of the yellow powder solid with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 446 nm was obtained by excitation at 315 nm.

(Example 5)
<Synthesis of YL7 and its fluorescence characteristics>
25 mL of methyl alcohol was added to 1.0 mmol of yttrium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Y), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 20 ml of a methanol solution containing 3.0 mmol of 5-bromosalicylaldehyde was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. During this time, a yellow precipitate was deposited. The solution was allowed to stand for 2 hours, and then the precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.59 g, and the yield was 75%. Elemental analysis values are C, 41.02% (calculated value 41.04%), H, 2.98% (calculated value 3.19%), N for C ₂₇ H ₂₄ N ₄ O ₃ Br ₃ Y · 0.5H ₂ O = 790.130 It was 6.95% (calculated value 7.09%). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1627 cm ^-1 . When the yellow powder was dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to YL7 + Na ⁺ was observed at 803 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, blue fluorescence was observed. In addition, blue fluorescence was also observed in the acetonitrile solution when irradiated with light at 365 nm. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 440 nm was obtained by excitation at 330 nm. As a result of measuring the fluorescence spectrum of the yellow powder solid with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 458 nm was obtained by excitation at 315 nm.

(Example 6)
<Synthesis of SmL1 and its fluorescence characteristics>
25 mL of methyl alcohol was added to 1.0 mmol of samarium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Sm), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of salicylaldehyde was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. During this time, a yellow precipitate was deposited. The solution was allowed to stand for 2 hours, and then the precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.51 g and the yield was 80%. Elemental analysis values are C, 52.72% (calculated value 52.72%), H, 4.78% (calculated value 4.90%), N, 8.54% for C ₂₇ H ₂₇ N ₄ O ₃ Sm · CH ₃ OH = 637.93 (Calculated value 8.78%). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1624 cm ^-1 . When the yellow powder was dissolved in acetonitrile and ESI-MS was measured, peaks corresponding to SmL1 + Na ⁺ were observed at 630 and 632 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, red fluorescence was observed. In addition, red fluorescence was also observed in the acetonitrile solution when irradiated with light at 365 nm. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, fluorescence spectra having peaks at 567, 612, and 655 nm were obtained by excitation at 398 nm. As a result of measuring the fluorescence spectrum of the solid yellow powder with a fluorescence spectrophotometer, fluorescence spectra having peaks at 568, 616, and 655 nm were obtained by excitation at 398 nm.

(Example 7)
<Synthesis of SmL2 and its fluorescence characteristics>
25 mL of methyl alcohol was added to 1.0 mmol of samarium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Sm), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of 3-methylsalicylaldehyde was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. During this time, a yellow precipitate was deposited. The solution was allowed to stand for 2 hours, and then the precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.21 g and the yield was 32%. Elemental analysis values are C ₃₀ H ₃₃ N ₄ O ₃ Sm = 647.97, C, 55.47% (calculated value 55.61%), H, 5.02% (calculated value 5.13%), N, 8.43% (calculated value 8.65) %). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1618 cm ^-1 . When the yellow powder was dissolved in acetonitrile and ESI-MS was measured, peaks corresponding to SmL2 + Na ⁺ were observed at 672, 674 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, red fluorescence was observed. In addition, red fluorescence was also observed in the acetonitrile solution when irradiated with light at 365 nm.

(Example 8)
<Synthesis of SmL3 (1) and its fluorescence characteristics>
25 mL of methyl alcohol was added to 1.0 mmol of samarium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Sm), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of 3-t-butylsalicylaldehyde was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. This solution was concentrated to about 15 ml and allowed to stand for 2 hours. The precipitate was collected by filtration, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.36 g, and the yield was 46%. Elemental analysis values are C, 59.98% (calculated value 60.04%), H, 6.57% (calculated value 6.76%), N, 7.06 for C ₃₉ H ₅₁ N ₄ O ₃ Sm · 0.5CH ₃ OH = 790.23 % (Calculated value 7.09%). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1618 cm ^-1 . When the yellow powder was dissolved in acetonitrile and ESI-MS was measured, peaks corresponding to SmL3 + H ⁺ were observed at 776 and 778 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, red fluorescence was observed. In addition, red fluorescence was also observed in the acetonitrile solution when irradiated with light at 365 nm. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, fluorescence spectra having peaks at 567, 576, 606, 617, and 656 nm were obtained by excitation at 366 nm. As a result of measuring the fluorescence spectrum of the solid of yellow powder with a fluorescence spectrophotometer, fluorescence spectra having peaks at 566, 576, 606, 616, and 655 nm were obtained by excitation at 315 nm.

Example 9
<Synthesis of SmL3 (2) and its fluorescence characteristics>
To 0.5 mmol of samarium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Sm) and 0.5 mmol of ligand (H ₃ L3), add 25 ml of methyl alcohol, and heat and stir at 50-60 ° C. While adding 2.0 mmol of triethylamine. This solution was heated and stirred at 50 to 60 ° C. for 5 minutes and then left in a cool dark place. The precipitate was collected by filtration, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. Yellow crystals were obtained by recrystallizing yellow powder from acetonitrile. The yield was 0.36 g, and the yield was 46%. The elemental analysis values are C, 60.30% (calculated value 60.50%), H, 6.79% (calculated value 6.64%), N, 7.07% (calculated value 7.24) for C ₃₉ H ₅₁ N ₄ O ₃ Sm = 774.21 %). Other properties were the same as in (Example 8).

(Example 10)
<Synthesis of SmL4 and its fluorescence characteristics>
25 mL of methyl alcohol was added to 1.0 mmol of samarium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Sm), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of 5-t-butylsalicylaldehyde was added, and the mixture was heated and stirred at 50-60 ° C. for 2 minutes. This solution was allowed to stand in a cool dark place for 3 hours, and then the precipitate was collected by filtration, washed with cold methanol, and dried under reduced pressure to obtain a yellow powder. The yield was 0.27 g and the yield was 33%. Elemental analysis values are C, 57.43% (calculated value 57.18%), H, 6.63% (calculated value 6.89%), N, 6.81 for C ₃₉ H ₅₁ N ₄ O ₃ Sm · 2.5H ₂ O = 819.25 % (Calculated value 6.84%). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1627 cm ^-1 . When the yellow powder was dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to SmL4 + Na ⁺ was observed at 798, 800 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, red fluorescence was observed. In addition, red fluorescence was also observed in the acetonitrile solution when irradiated with light at 365 nm. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, fluorescence spectra having peaks at 567, 617, and 656 nm were obtained by excitation at 366 nm.

(Example 11)
<Synthesis of SmL5 and its fluorescence characteristics>
20 ml of methyl alcohol was added to 1.0 mmol of samarium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Sm), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 8 ml of a methanol solution containing 3.0 mmol of 3,5-Di-t-butylsalicylaldehyde was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. This solution was concentrated to about 15 ml and allowed to stand for 2 hours. The precipitate was collected by filtration, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.31 g, and the yield was 32%. Elemental analysis values are C, 63.94% (calculated value 63.77%), H, 7.85% (calculated value 8.08%), N, 5.77% for C ₅₁ H ₇₅ N ₄ O ₃ Sm · H ₂ O = 960.54 (Calculated value 5.83%). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1617 cm ^-1 . When yellow powder was dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to SmL5 + H ⁺ was observed at 945, 947 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, red fluorescence was observed. In addition, red fluorescence was also observed in the acetonitrile solution when irradiated with light at 365 nm.

(Example 12)
<Synthesis of EuL1 and its fluorescence characteristics>
To 1.0 mmol of europium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Eu) was added 25 ml of methyl alcohol, and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of salicylaldehyde was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. During this time, a yellow precipitate was deposited. The solution was allowed to stand for 2 hours, and then the precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.44 g and the yield was 72%. The elemental analysis values are C ₂₇ H ₂₇ N ₄ O ₃ Eu = 607.49, C, 53.26% (calculated value 53.38%), H, 4.42% (calculated value 4.48%), N, 9.03% (calculated value 9.22) %). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1630 cm ^-1 . When the yellow powder was dissolved in acetonitrile and ESI-MS was measured, peaks corresponding to EuL1 + Na ⁺ were observed at 629 and 631 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, red fluorescence was observed. However, when the acetonitrile solution was irradiated with 365 nm light, no fluorescence was observed with the naked eye. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having a very small peak at 610 nm was obtained by excitation at 380 nm. In acetonitrile, considerable quenching occurred, and it seems that no fluorescence was observed with the naked eye. As a result of measuring the fluorescence spectrum of the yellow powder solid with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 609 nm was obtained by excitation at 402 nm.

(Example 13)
<Synthesis of TbL1 and its fluorescence characteristics>
25 ml of methyl alcohol was added to 1.0 mmol of terbium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Tb), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of salicylaldehyde was added, and the mixture was heated and stirred at 50-60 ° C. for 2 minutes. This solution was allowed to stand for 2 hours. The resulting precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.54 g and the yield was 88%. Elemental analysis values are C ₂₇ H ₂₇ N ₄ O ₃ Tb = 614.45, C, 52.49% (calculated 52.78%), H, 4.43% (calculated value 4.43%), N, 8.82% (calculated value 9.12% ) In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1629 cm ^-1 . When the yellow powder was dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to TbL1 + Na ⁺ was observed at 637 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, green fluorescence was observed. However, when the acetonitrile solution was irradiated with 365 nm light, no fluorescence was observed with the naked eye. On the other hand, when the acetonitrile solution was irradiated with light of 254 nm, very weak fluorescence was observed. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having a very small peak at 547 nm was obtained by excitation at 382 nm. In acetonitrile, considerable quenching occurred, and it seems that almost no fluorescence was observed with the naked eye. As a result of measuring the fluorescence spectrum of the yellow powder solid with a fluorescence spectrophotometer, fluorescence spectra having peaks at 490, 547, 583, and 621 nm were obtained by excitation at 393 nm.

(Example 14)
<Synthesis of TbL3 and its fluorescence characteristics>
25 ml of methyl alcohol was added to 1.0 mmol of terbium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Tb), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of 3-t-butylsalicylaldehyde was added, and the mixture was heated and stirred at 50 to 60 ° C. for 5 minutes. This solution was allowed to stand for 3 weeks. The resulting precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain yellow crystals. The yield was 0.66 g and the yield was 84%. Elemental analysis values are C, 59.77% (calculated 59.84%), H, 6.48% (calculated value 6.57%), N, 7.06% (calculated value 7.16%) for C ₃₉ H ₅₁ N ₄ O ₃ Tb = 782.67 ) In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1619 cm ^-1 . When yellow crystals were dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to TbL3 + H ⁺ was observed at 783 (m / z). When yellow crystals were irradiated with 365 nm light from an ultraviolet lamp, green fluorescence was observed. However, when the acetonitrile solution was irradiated with 365 nm light, no fluorescence was observed with the naked eye. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having a very small peak at 550 nm was obtained by excitation at 366 nm. As a result of measuring the fluorescence spectrum of the yellow crystalline solid with a fluorescence spectrophotometer, fluorescence spectra having peaks at 487, 497, and 550 nm were obtained by excitation at 315 nm.

(Example 15)
<Synthesis of Y _n Eu _1-n L1 and its fluorescence characteristics>
25 ml of methyl alcohol was added to 0.5 mmol of yttrium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Y) and 0.5 mmol of europium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Eu), Heated and stirred at ~ 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of salicylaldehyde was added, and the mixture was heated and stirred at 50-60 ° C. for 2 minutes. During this time, a yellow precipitate was deposited. The solution was allowed to stand for 2 hours, and then the precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.46 g, and the yield was 78%. Elemental analysis values are C ₂₇ H ₂₇ N ₄ O ₃ Y _0.55 Eu _0.45・ 0.5CH ₃ OH = 588.83, C, 56.03% (calculated value 56.09%), H, 4.70% (calculated value 4.96%), N, 9.51% (calculated value 9.52%). The content and ratio of the metal were determined by dissolving yellow powder in dilute hydrochloric acid and measuring it at 371.029 nm (Y) and 381.965 nm (Eu) by ICP emission spectrophotometry. Y, 8.35% (calculated value 8.30% ), Eu, 11.79% (calculated value 11.61%). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1629 cm ^-1 . The yellow powder was dissolved in acetonitrile, was measured ESI-MS, 567 (m / z) to a peak corresponding to YL1 + Na ⁺ is, a peak corresponding to EuL1 ⁺ Na + to 629, 631 (m / z) Was observed. When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, red fluorescence was observed. On the other hand, blue fluorescence was observed in the acetonitrile solution when irradiated with light of 365 nm. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 433 nm was obtained by excitation at 330 nm. As a result of measuring the fluorescence spectrum of the yellow powder solid with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 609 nm was obtained by excitation at 434 nm.

(Example 16)
<Synthesis of Y _n Tb _1-n L1 and its fluorescence characteristics>
25 ml of methyl alcohol was added to 0.5 mmol of yttrium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Y) and 0.5 mmol of terbium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Tb), Heated and stirred at ~ 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of salicylaldehyde was added, and the mixture was heated and stirred at 50-60 ° C. for 2 minutes. During this time, a yellow precipitate was deposited. The solution was allowed to stand for 2 hours, and then the precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.48 g, and the yield was 81%. Elemental analysis values are C, 55.38% (calculated value 55.60%), H, 4.63% (calculated value 4.92%), C ₂₇ H ₂₇ N ₄ O ₃ Y _0.52 Tb _0.48・ 0.5CH ₃ OH = 594.06, N, 9.44% (calculated value: 9.43%). Regarding the content and ratio of metals, the yellow powder was dissolved in dilute hydrochloric acid solution and measured by ICP emission spectrophotometry at 371.029 nm (Y) and 367.635 nm (Tb), Y, 8.04% (calculated value 7.78% ), Tb, 12.52% (calculated value 12.84%). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1631 cm ^-1 . The yellow powder was dissolved in acetonitrile, was measured ESI-MS, 567 peak corresponding to (m / z) in YL1 + Na ⁺ is observed a peak corresponding to TBL1 + Na ⁺ to 637 (m / z) It was done. When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, green fluorescence was observed. On the other hand, blue fluorescence was observed in the acetonitrile solution when irradiated with light of 365 nm. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 432 to 433 nm was obtained by excitation at 313, 333, and 381 nm. As a result of measuring the fluorescence spectrum of the solid yellow powder with a fluorescence spectrophotometer, fluorescence spectra having peaks at 490, 548, 583, and 621 nm were obtained by excitation at 376 nm.

(Example 17)
<Synthesis of Eu _n Tb _1-n L1 and its fluorescence characteristics>
50 ml of methyl alcohol was added to 0.5 mmol of europium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Eu) and 0.5 mmol of terbium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Tb) to give 50 Heated and stirred at ~ 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (2-aminoethyl) amine was added and heated and stirred at 50-60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of salicylaldehyde was added, and the mixture was heated and stirred at 50-60 ° C. for 2 minutes. During this time, a yellow precipitate was deposited. The solution was allowed to stand for 2 hours, and then the precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.46 g, and the yield was 75%. The elemental analysis values are C ₂₇ H ₂₇ N ₄ O ₃ Eu _0.46 Tb _0.54 = 611.25, C, 52.93% (calculated value 53.05%), H, 4.39% (calculated value 4.45%), N, 8.96% ( The calculated value was 9.17%). Regarding the content and ratio of the metal, the yellow powder was dissolved in dilute hydrochloric acid solution and measured by ICP emission spectrophotometry at 381.965 nm (Eu) and 367.635 nm (Tb) .Eu, 11.52% (calculated value 11.44% ), Tb, 14.41% (calculated value 14.04%). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1629 cm ^-1 . The yellow powder was dissolved in acetonitrile, was measured ESI-MS, 629, 631 peak corresponding to (m / z) in EuL1 ⁺ Na + is, a peak corresponding to TBL1 + Na ⁺ to 637 (m / z) Was observed. When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, red fluorescence was observed. However, when the acetonitrile solution was irradiated with 365 nm light, no fluorescence was observed with the naked eye. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having very small peaks at 547 and 610 nm was obtained by excitation at 380 nm. In acetonitrile, considerable quenching occurred, and it seems that no fluorescence was observed with the naked eye. As a result of measuring the fluorescence spectrum of the yellow powder solid with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 609 nm was obtained by excitation at 434 nm.

(Example 18)
_{<Y m Eu n Tb 1- (} m + n) L1 Synthesis and fluorescent properties of>
0.5 mmol of yttrium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Y), 0.5 mmol of europium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Eu), and terbium trifluoromethanesulfonate ((CF ₃ 37.5 ml of methyl alcohol was added to 0.5 mmol of SO ₃ ) ₃ Tb), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 7.5 ml of a methanol solution containing 3.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 7.5 ml of methanol solution containing 4.5 mmol of salicylaldehyde was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. During this time, a yellow precipitate was deposited. The solution was allowed to stand for 2 hours, and then the precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.68 g, and the yield was 74%. Elemental analysis values for C ₂₇ H ₂₇ N ₄ O ₃ Y _0.40 Eu _0.28 Tb _0.32・ CH ₃ OH = 616.54, C, 54.38% (calculated value 54.55%), H, 4.94% (calculated value 5.07%) N, 8.95% (calculated value 9.09%). Regarding the content and ratio of the metal, the yellow powder was dissolved in dilute hydrochloric acid aqueous solution and measured by ICP emission spectrophotometry at 371.029 nm (Y), 381.965 nm (Eu), 367.635 nm (Tb). % (Calculated value 5.77%), Eu, 6.77% (calculated value 6.90%), Tb, 8.36% (calculated value 8.25%). In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1631 cm ^-1 . The yellow powder was dissolved in acetonitrile, was measured ESI-MS, 567 (m / z) to a peak corresponding to YL1 + Na ⁺ is, a peak corresponding to EuL1 ⁺ Na + to 629, 631 (m / z) However, a peak corresponding to TbL1 + Na ⁺ was observed at 637 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, red fluorescence was observed. On the other hand, blue fluorescence was observed in the acetonitrile solution when irradiated with light of 365 nm. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 433 nm was obtained by excitation at 330 nm. As a result of measuring the fluorescence spectrum of the yellow powder solid with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 609 nm was obtained by excitation at 434 nm.

(Example 19)
_{<Y m Sm n Tb 1- (} m + n) L3 Synthesis and fluorescent properties of>
Yttrium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Y) 1.0 mmol, samarium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Sm) 1.0 mmol, and terbium trifluoromethanesulfonate ((CF ₃ To ₃₀ mmol of SO ₃ ) ₃ Tb), 60 ml of methyl alcohol was added and heated and stirred at 50-60 ° C. To this solution, 10 ml of a methanol solution containing 6.0 mmol of tris (2-aminoethyl) amine was added, and the mixture was heated and stirred at 50-60 ° C. for 2 minutes. Further, 10 ml of a methanol solution containing 9.0 mmol of 3-t-butylsalicylaldehyde was added, and the mixture was heated and stirred at 50-60 ° C. for 2 minutes. This solution was concentrated to about 40 ml and allowed to stand for 2 hours. The precipitate was collected by filtration, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.63g. The yellow powder was dissolved in dilute hydrochloric acid solution and measured at 371.029 nm (Y), 442.434 nm (Sm), and 367.635 nm (Tb) by ICP emission spectrophotometry. Y: Sm: Tb = 1.13: 1.65: 1.00 became. In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1619 cm ^-1 . The yellow powder was dissolved in acetonitrile, was measured ESI-MS, the 713 (m / z), peak corresponding to YL1 + H ⁺ is 776, the 778 (m / z), corresponding to SML1 + H ⁺ A peak corresponding to TbL1 + H ⁺ was observed at 783 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, red fluorescence was observed. On the other hand, blue fluorescence was observed in the acetonitrile solution when irradiated with light of 365 nm. As a result of measuring the fluorescence spectrum of the acetonitrile solution with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 450 nm was obtained by excitation at 331 nm. As a result of measuring the fluorescence spectrum of the solid yellow powder with a fluorescence spectrophotometer, fluorescence spectra having peaks at 566 nm, 615 nm, and 654 nm were obtained by excitation at 434 nm.

(Example 20)
<Synthesis of YL8 and its fluorescence characteristics>
25 mL of methyl alcohol was added to 1.0 mmol of yttrium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Y), and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (3-aminopropyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of salicylaldehyde was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. This solution was concentrated to about 10 milliliters, the precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.27g. In the infrared absorption spectrum, a peak due to C = N stretching vibration was observed at 1632 cm ^-1 . When yellow powder was dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to YL8 + H ⁺ was observed at 587 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, blue fluorescence was observed. In addition, blue fluorescence was also observed in the acetonitrile solution when irradiated with light at 365 nm.

(Example 21)
<Synthesis of EuL8 and its fluorescence characteristics>
To 1.0 mmol of europium trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₃ Eu) was added 25 ml of methyl alcohol, and the mixture was heated and stirred at 50 to 60 ° C. To this solution, 5 ml of a methanol solution containing 2.0 mmol of tris (3-aminopropyl) amine was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. Further, 5 ml of a methanol solution containing 3.0 mmol of salicylaldehyde was added, and the mixture was heated and stirred at 50 to 60 ° C. for 2 minutes. This solution was concentrated to about 10 milliliters, the precipitate was filtered off, washed with cold methanol, and then dried under reduced pressure to obtain a yellow powder. The yield was 0.26g. In the infrared absorption spectrum, a peak based on C = N stretching vibration was observed at 1627 cm ^-1 . When the yellow powder was dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to EuL8 + H ⁺ was observed at 649, 651 (m / z). When yellow powder was irradiated with 365 nm light from an ultraviolet lamp, red fluorescence was observed.

(Example 22)
<Thermal stability of YL1>
YL1 synthesized in (Example 1) was placed in an oven capable of temperature control and kept at 250 ° C. for 1 hour. After returning the temperature to room temperature, YL1 was taken out and analyzed. When YL1 was heated and dissolved in acetonitrile, and ESI-MS was measured, a peak corresponding to YL1 + Na ⁺ was observed at 567 (m / z), and it was confirmed that there was no change before and after heating. . When YL1 that had been heated was irradiated with 365 nm light from an ultraviolet lamp, blue fluorescence was observed. Even in the acetonitrile solution, blue fluorescence was observed by light irradiation at 365 nm. As a result of measuring the fluorescence spectrum of the solid with a fluorescence spectrophotometer, it was confirmed that a fluorescence spectrum having a peak at 432 nm was obtained by excitation at 330 nm, and that there was almost no change before and after heating.

(Example 23)
<Thermal stability of EuL1>
EuL1 synthesized in Example 12 was placed in an oven capable of temperature control and kept at 250 ° C. for 1 hour. After returning the temperature to room temperature, EuL1 was taken out and analyzed. When heated EuL1 was dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to EuL1 + Na ⁺ was observed at 629, 631 (m / z), indicating that there was no change before and after heating. confirmed. When EuL1 that had been heated was irradiated with 365 nm light from an ultraviolet lamp, red fluorescence was observed. As a result of measuring the fluorescence spectrum of the solid with a fluorescence spectrophotometer, it was confirmed that a fluorescence spectrum having a peak at 608 nm was obtained by excitation at 402 nm, and there was almost no change before and after heating.

(Example 24)
<Thermal stability of TbL1>
TbL1 synthesized in (Example 13) was placed in an oven capable of temperature control and kept at 250 ° C. for 1 hour. After returning the temperature to room temperature, TbL1 was taken out and analyzed. When heated TbL1 was dissolved in acetonitrile and ESI-MS was measured, a peak corresponding to TbL1 + Na ⁺ was observed at 637 (m / z), and it was confirmed that there was no change before and after heating. . When TbL1 that had been heated was irradiated with 365 nm light from an ultraviolet lamp, green fluorescence was observed. As a result of measuring the fluorescence spectrum of a solid with a fluorescence spectrophotometer, it was confirmed that excitation with 393 nm gave fluorescence spectra with peaks at 491, 547, 586, and 621 nm, and there was almost no change before and after heating. .

(Example 25)
<Fluorescence spectrum of resin composition containing fluorescent metal complex>
A glass plate was placed on a hot plate whose surface temperature was set to 130 to 140 ° C., and 0.5 g of a commercially available low density polyethylene was placed thereon. This was stretched with a glass rod to make it sufficiently soft, and 0.012 mmol of YL1, or EuL1, or TbL1 was added as a solid. After kneading for about 20 minutes on a glass plate, stretch and flatten, cover with a new glass plate from above, sandwich low density polyethylene containing metal complex between two glass plates, and evenly force from both sides Was added to make the thickness uniform. After returning to room temperature, the glass plate was peeled off to obtain a resin composition containing a fluorescent metal complex. When the resin composition containing YL1, EuL1, or TbL1 was irradiated with 365 nm light from an ultraviolet lamp, blue, red, and green fluorescence were observed, respectively. As a result of measuring the fluorescence spectrum of the resin composition containing the fluorescent metal complex with a fluorescence spectrophotometer, a fluorescence spectrum having a peak at 420 nm is obtained by excitation at 330 nm in the case of YL1, and in the case of EuL1. , A fluorescence spectrum having a peak at 608 nm was obtained by excitation at 402 nm, and in the case of TbL1, fluorescence spectra having peaks at 491, 548, 586, and 622 nm were obtained by excitation at 393 nm. The spectrum pattern in any case was almost the same as the solid fluorescence spectrum pattern of the fluorescent metal complex.

  The light-emitting material of the present invention not only emits fluorescence in solid or solution upon irradiation with excitation light, but also has high compatibility with the resin, and a fluorescent resin composition with good dispersibility can be obtained. It can be used for display devices such as printing ink, PDP and FED, and light emitting devices such as white LEDs. In particular, by using a blue light emitting material made of yttrium complex, a red light emitting material made of europium complex or samarium complex, and a green light emitting material made of terbium complex as the three primary colors of light, a good white LED with little change in white hue can be obtained. In addition, since the phosphor layer can be thinned because it can be dispersed in the resin in an ultrafine particle state, the display device and the light emitting device can be thinned. In addition, since it can emit light in the vicinity of 450 nm and 660 nm, which is necessary for plant growth, it is expected to be used in plant factories. Further, it can be used as a fluorescent labeling agent by utilizing the fluorescence characteristics in a solution state. I can expect.

The figure which shows the fluorescence spectrum of YL1. The figure which shows the fluorescence spectrum of SmL1, EuL1, and TbL1. The figure which shows the result of the thermogravimetry (TG) and differential thermal analysis (DTA) of EuL1. The figure which shows the result of the thermogravimetry (TG) and differential thermal analysis (DTA) of YL1. The figure which shows the result of the thermogravimetry (TG) and differential thermal analysis (DTA) of TbL1. The figure which shows the fluorescence spectrum after heating YL1, TbL1, EuL1 at 250 degreeC for 1 hour, and returning to room temperature. The figure which shows the fluorescence spectrum of the resin sheet containing YL1, TbL1, and EuL1.

Claims (5)

The following general formula (I)

(Wherein, M represents yttrium beam, R ₁ and R ₂ are hydrogen atoms, at least one member selected alkyl group which may have a branch having 1 to 4 carbon atoms, and from the group consisting of halogen atoms Represents one.)
Or the following general formula (II)

(Wherein, M represents yttrium beam, R ₁ and R ₂ are hydrogen atoms, at least one member selected alkyl group which may have a branch having 1 to 4 carbon atoms, and from the group consisting of halogen atoms Represents one.)
A luminescent material comprising a rare earth metal complex represented by the formula: The following general formula (I)

(In the formula, M represents at least one metal selected from yttrium and a lanthanoid , R ₁ and R ₂ represent a hydrogen atom, an alkyl group optionally having 1 to 4 carbon atoms, and a halogen atom. Represents at least one selected from the group consisting of atoms.)
Or the following general formula (II)

(In the formula, M represents at least one metal selected from yttrium and a lanthanoid , R ₁ and R ₂ represent a hydrogen atom, an alkyl group optionally having 1 to 4 carbon atoms, and a halogen atom. Represents at least one selected from the group consisting of atoms.)
A luminescent material comprising a rare earth metal complex represented by the formula: As a light emitting material contained in the resin, the resin composition characterized by containing a luminescent material according to claim 1 or claim 2. As a light emitting material contained in the resin, and blue-emitting materials of 請 Motomeko 1, wherein said general formula (I) or M in the general formula (II) is Ru europium or samarium der red luminescent material, resin composition, characterized in that said M in the general formula (I) or the general formula (II) contains the terbium der Ru green luminescent material.   The resin composition according to claim 3 or 4, wherein the resin is an olefin resin.

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