JP2010174052A - Luminous transition metal complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphor or a phosphorescent substance for excitable light-emitting devices comprising a transition metal complex, a method for producing the same, and a light-emitting device using the same. <P>SOLUTION: The transition metal complex for light-emitting devices is obtained by bonding 2-3 ligands to a transition metal and the transition metal complex can be used as a novel useful light-emitting device since it has light-emitting properties different from the conventional ones. Further, since the ligands are formed of organic substances, the transition metal complex can be made into a light-emitting device by freely changing the form to become industrially very useful. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a phosphor or phosphor for an excited light-emitting device comprising a transition metal complex, a method for producing the same, and a light-emitting device using the same.

The present invention relates to a phosphor or phosphor suitable as a light-emitting element used for an LED or the like.

The phosphor or phosphor according to the present invention can be provided as a light-emitting element for LED, and can also be applied to a liquid crystal backlight or a CRT light-emitting element in other lighting applications and display device fields. be able to. Furthermore, it can be applied to electronic display devices such as FED (field emission display), PDP (plasma display), EL (electroluminescence) and the like.

As a light emitter for LED, a light emitter made of a solid (powder) of an inorganic compound is used (for example, refer to Patent Document 1), but the light emitter is kneaded into a polymeric resin to obtain a resin composition. Since the resin composition is coated and molded on the excitation light emitting element part, the light emitter has high affinity for members such as a polymeric resin, is easy to process, and dissolves in a solvent. There has been a demand for an organic light-emitting body having a high degree of freedom of shape change such as coating.

JP 2004-63239 A JP 2005-255773 A JP 2006-193573 A

An object of the present invention is to provide a phosphor or phosphor for an excitation light-emitting device comprising a transition metal complex.

Under these circumstances, the present inventors have intensively studied a luminescent material composed of a transition metal complex in order to solve the above-mentioned problems. It has been found that the transition metal complex having a coordinate bond is excited by ultraviolet rays and emits light (see Patent Documents 2 and 3).

Furthermore, as a result of research on phosphors composed of transition metal complexes, luminescent transition metal complexes characterized by having the structure represented by the formula (1) exhibit characteristic luminescent properties, particularly two-coordination. It has been found that the bonded transition metal complex is a phosphor or phosphor having useful emission characteristics.

(1)
(In the formula (1), M is any of transition metal ions of Cu, Zn, Ag, Cd, Au, Hg, Pt, and Pd, and the coordinating group L ₁ or L ₂ is X or M. A heterocycle having a coordinated Y and Z, the heterocycle may or may not form a condensed ring structure, X is a halide ion or counter anion ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ^-
, CF ₃ SO ₃ ^— , B (C ₆ H ₅ ) ₄ ^— , but L ₁ and L ₂ are not both X. Y is an atom of N, S, P, or O. Z is —CR ³ ═CR ⁴ —, —N═CR ⁵ —, —NR ⁶ —, or —O—. Here, when L _n is X, there may be no linker coupled to L _n . R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom or an organic group having 1 to 20 carbon atoms. R ¹ is a hydrogen atom, a halogen atom or an organic group having 1 to 20 carbon atoms, and R ² is a hydrogen atom, a halogen atom or an organic group having 1 to 20 carbon atoms. When any of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ forms a condensed ring structure, ^{2 of} R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ Two or more may be connected to each other to form a ring. Linker is a linear or branched alkylene group having 1 to 20 carbon atoms, and one or two or more methylene groups in the alkylene group are -O-, -CO-,- Any one or more of O—CO—, —CH═CH—, —C≡C—, —N═N— may be substituted, and a hydrogen atom in the alkylene group may be substituted with a halogen atom; Also good. basement is a hydrocarbon group having 1 to 30 carbon atoms or a hetero compound residue containing 1 or more selected from the group consisting of N, S, P, and O, and having 1 to 30 carbon atoms. To express. T _n is an n organic group bonded to the basement, and is a linear or branched alkyl group having 1 to 20 carbon atoms, and the methylene group and the hydrogen atom in the alkyl group are the above linker It may be substituted in the same manner as in. n is an integer of 0 or more and 5 or less. When there are a plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, Y, Z, linker, and basement, these are independent of each other. )

The transition metal complex for a light-emitting device of the present invention is a complex having 2-3 coordination bonds, and can be used as a useful light-emitting device because it has a light-emitting characteristic different from that of a conventional transition metal complex. Since the ligand is made of an organic substance, the shape can be freely changed and the element can be installed in the device, which is extremely useful industrially.

It is a figure which shows the basic structure of a luminescent transition metal complex. 1,3,5-tris (2- (6-methyl-2-pyridinyl) ethyl) -2,4,6-triethylbenzene (Com-1) and a two-coordinate copper complex having a chlorine atom as a ligand It is a figure which shows a three-dimensional structural formula. It is a figure which shows the three-dimensional structural formula of the 2 coordination copper complex which makes a 1,3,5-tris (2- (2-pyridinyl) ethyl) -2,4,6-triethylbenzene and a chlorine atom a ligand. 1,3,5-tris (2- (6-methyl-2-pyridinyl) ethyl) -2,4,6-triethylbenzene (Com-1) and a two-coordinate copper complex having a chlorine atom as a ligand It is a figure which shows a light emission characteristic.

The present invention is described in detail below. In the present invention, the luminescent transition metal complex having the structure represented by the formula (1) is a phosphor or phosphor having a characteristic luminescent property.

(1)
(In the formula (1), M is any of transition metal ions of Cu, Zn, Ag, Cd, Au, Hg, Pt, and Pd, and the coordinating group L ₁ or L ₂ is X or M. A heterocycle having a coordinated Y and Z, the heterocycle may or may not form a condensed ring structure, X is a halide ion or counter anion ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ^-
, CF ₃ SO ₃ ^— , B (C ₆ H ₅ ) ₄ ^— , but L ₁ and L ₂ are not both X. Y is an atom of N, S, P, or O. Z is —CR ³ ═CR ⁴ —, —N═CR ⁵ —, —NR ⁶ —, or —O—. Here, when L _n is X, there may be no linker coupled to L _n . R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom or an organic group having 1 to 20 carbon atoms. R ¹ is a hydrogen atom, a halogen atom or an organic group having 1 to 20 carbon atoms, and R ² is a hydrogen atom, a halogen atom or an organic group having 1 to 20 carbon atoms. When any of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ forms a condensed ring structure, ^{2 of} R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ Two or more may be connected to each other to form a ring. Linker is a linear or branched alkylene group having 1 to 20 carbon atoms, and one or two or more methylene groups in the alkylene group are -O-, -CO-,- Any one or more of O—CO—, —CH═CH—, —C≡C—, —N═N— may be substituted, and a hydrogen atom in the alkylene group may be substituted with a halogen atom; Also good. basement is a hydrocarbon group having 1 to 30 carbon atoms or a hetero compound residue containing 1 or more selected from the group consisting of N, S, P, and O, and having 1 to 30 carbon atoms. To express. T _n is an n organic group bonded to the basement, and is a linear or branched alkyl group having 1 to 20 carbon atoms, and the methylene group and the hydrogen atom in the alkyl group are the above linker It may be substituted in the same manner as in. n is an integer of 0 or more and 5 or less. When there are a plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, Y, Z, linker, and basement, these are independent of each other. )

The coordinating group L _n in the formula (1) represents a heterocyclic structure having X or Y and Z, and may or may not form a condensed ring structure with the heterocyclic ring. X is a halide ion such as F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , or counter anion ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ^{−
_{, CF 3 SO 3 -, B}} (C 6 H 5) 4 - are preferred one or more selected from, Cl ^- species are most preferred.

The number of X coordinated to M is 0 or 1, and when L _n is X, there is no need for a linker.

When M in the formula (1) is a copper ion having a two-coordinate bond, there is a characteristic that the ligand, copper and the ligand are specifically arranged on a substantially straight line.

Specific examples of the heterocyclic structure having Y and Z include pyrrole, indole, carbazole, imidazole, pyrazole, pyridine, bipyridine, quinoline, isoquinoline, acridine, pyridazine, pyrimidine, pyrazine, triazine, phthalazine, quinazoline, and quinoxaline. In addition, the nitrogen-containing heterocycle may be a heterocycle containing an oxygen atom, oxazole, oxazene, oxazine, and further containing a sulfur atom, and examples thereof include thiazole and benzothiazole.
Any hydrogen atom bonded to each of these heterocycles may be bonded to another substituent R ¹ or R ² .

As the substituent R ¹ or R ² , a fluorine group, (—F), chlorine group (—Cl), bromine group (—Br), iodine group (—I), methyl group (—CH ₃ ), ethyl group ( -CH ₂ CH _3), propyl _{(-CH 2 CH 2 CH 3)} , isopropyl group _{(-CH (CH 3) 2)} , t- butyl group _{(-C (CH 3) 3)} , dimethylamino group (- N _{(CH 3) 2),} etc. methoxy group (-OCH ₃₎ and the like.

Among them, also 6-methylpyridine residues in a nitrogen-containing heterocyclic compound is most preferred as L _n.

Linker in Formula (1) is a linear or branched alkylene group having 1 to 20 carbon atoms, and one or two or more methylene groups not adjacent to the alkylene group are -O-, Any one or more of -CO-, -O-CO-, -CH = CH-, -C≡C-, and -N = N- may be substituted, and the hydrogen atom in the alkylene group is a halogen atom. It may be replaced with an atom. The alkylene group preferably has 1 to 15 carbon atoms, more preferably 1 to 10, and still more preferably 1 to 5. Most preferably 2, it is an ethylene group. However, when L _n in the formula (1) is X, there is no need for the linker.

The n T _n which are coupled to the basement, independently of one another in the formula (1), T _n is a straight-chain or branched alkyl group ranging from 1 to 20 carbon atoms, a methylene in the alkyl group The group and the hydrogen atom may be substituted in the same manner as in the above linker. The number of carbon atoms of the alkyl group is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 5. The case of 2 is most preferable, that is, the case where T _n is an ethyl group.

_N in Tn is the number of organic groups T bonded to the basement, and is an integer in the range of 0 to 5. When n is 0, T means a hydrogen atom. n is preferably in the range of 2 to 6, and most preferably 3.

The basement in the formula (1) contains a hydrocarbon group having 1 to 30 carbon atoms or one or more selected from the group consisting of N, S, P, and O, and having 1 to 30 carbon atoms. It represents a hetero compound residue and has a valence of (n + 3). The base is a linear or branched alkylene group, an aromatic hydrocarbon a residue (a = n + 3) and a hetero compound containing one or more atoms selected from the group consisting of N, S, P, and O. Residue (a = n + 3). The alkylene group preferably has a cyclic structure rather than a linear or branched chain structure represented by the general formula, — (CH ₂ ) _k — (k is 1 or more and 30 or less). Specifically, Examples include cyclohexane a residue and adamantane a residue. Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, pyrene, and perylene. Examples of the hetero compound having one or more selected from the group consisting of N, S, P, and O include pyridine, furan, thiophene, and the like. Of these compounds, aromatic hydrocarbons are preferred and benzene is most preferred.

As a ligand, a compound consisting of a combination of L _n : 6-methylpyridine 1 residue, basement 6 residues of benzene, linker: ethylene group, T _n : ethyl group (n = 3) has a characteristic light emitting property. More preferably, most preferably the linker ethylene group is bonded to the 1, 3, 5 position of the benzene ring of the basement, and the ethyl group of T is bonded to the 2, 4, 6 position of the benzene ring of the basement, L _n of 6-methylpyridin-1 compounds linker is attached to the 2-position of the residue (1,3,5-tris (2- (6-methyl-2-pyridinyl) ethyl) -2,4,6 Triethylbenzene: Com-1).

Com-1
Me in the chemical formula of Com-1 represents a methyl group.

In the transition metal complex forming the phosphor of the present invention, a quasi-monomolecular structure composed of a transition metal ion and a ligand may be formed, but the ligand coordinate bond portion faces the outside of the molecule. Then, it may be coordinated with a metal ion to form a multidimensional divergent coordinate bond.

Next, the manufacturing method of the excitation light-emitting body of this invention is demonstrated.
First, the ligand used in the luminescent material of the present invention can be synthesized as follows, but the synthesis method is not limited thereto.

For example, the most preferred compound is 1,3,5-tris (2- (6-methyl-2-pyridinyl) ethyl) -2,4,6-ethylbenzene as _{L n} constituting the phosphor of the present invention, the following It can be synthesized according to the scheme of
By reacting 1,3,5-triethylbenzene in the presence of formaldehyde, zinc, hydrobromic acid and acetic acid at 95 ° C. according to the following formula (2), 1,3,5-tris (bromomethyl) -2, 4,6-triethylbenzene can be synthesized (reference:
C. Walsdorf, et al. , J .; Chem. Res. 1996, (S) 282, (M) 1601-1609).
(2)

Then, 2,6-dimethylpyridine in THF was lithiated with n-butyllithium at −80 ° C., and this was synthesized with 1,3,5-tris (bromomethyl) -2,4, By reacting 6-triethylbenzene according to the following formula (3), the desired 1,3,5-tris (2- (6-methyl-2-pyridinyl) ethyl) -2,4,6-triethylbenzene is obtained. Can be synthesized.
(3)

The transition metal complex is weighed so that the molar ratio of the ligand and metal salt constituting the target transition metal complex is a predetermined ratio. Acetonitrile, ethyl acetate, methylene chloride, etc. can be used for the ligand, and the like can be dissolved in a liquid phase diffusion method to prepare crystals. Further, for example, a crystalline solid can be obtained by dissolving in a solvent such as acetonitrile in a minimum amount by heating and cooling the solution. It is also possible to obtain a crystalline solid by dissolving with an excess amount of solvent and then reducing the solubility by reducing the temperature by evaporating the solvent, or evaporating the solvent, or adding a poor solvent (such as methanol). it can. When the transition metal ion is likely to be oxidized, the anaerobic atmosphere (for example, by using a glove box or the like, the O ₂ concentration can be less than 1 volume ppm and the H ₂ O concentration can be less than 1 volume ppm). Preferably it is done. However, for example, when the transition metal ion is a copper ion and the counter anion is a chloride ion, the anaerobic atmosphere may not be required. At this time, CuCl can be used as a copper ion source. And the crystal | crystallization of the obtained copper complex can be taken out by filtration and you may wash | clean.

The copper salt, the coordinating organic compound, and the solvent used as starting materials for preparing the transition metal complex of the present invention preferably have a high purity (98% or more).
A glassy reaction vessel containing a glass tube or a glass-lined reaction vessel is used for the preparation of the ligand or complex, and the stirring medium is a fluororesin-coated stirrer, glass or glass-lined stirring blade Can be used.

The ligand constituting the luminescent material of the present invention can be dissolved in a temperature range from room temperature to 20 ° C. higher than the boiling point of the solvent. If it is higher than the boiling point, attach a reflux device.

In order to make the light emitter of the present invention exist in a polymer (including a resin), a transition metal salt and a low-molecular organic compound serving as a ligand coexist in the polymer solution, and the solvent is distilled off. Is possible. In addition, the transition metal complex may be made into powder and kneaded and dispersed in the polymer.

Transition metal complexes can be identified directly or indirectly using structural analysis devices such as elemental analysis, mass spectrometry, IR, UV-vis, fluorescence measurement, ESR, XRD, 4-axis, ion plate method, etc. Is possible.

Furthermore, the transition metal complex obtained by the above method can be pulverized by using a pulverizer that is usually used industrially, such as a ball mill, a vibration mill, an attritor, or a jet mill. Moreover, it can classify and can arrange a particle size. For atomization, fine droplets of the complex solution may be prepared by electrostatic spraying or an emulsion method and dried.

The luminescent material comprising the transition metal complex of the present invention can be used for, for example, a mercury-free fluorescent lamp disclosed in JP-A-2003-272527. Here, the luminous body is applied by pouring the solution of the luminous body of the present invention made of a copper complex into a glass pipe and drying, or by applying a slurry in which the luminous body is dispersed in a solvent and drying the solvent. Thus, the light emitting layer is formed. Thereafter, the end of the glass pipe is sealed, and after the rare gas is sealed, the other end is also sealed and sealed. Thereafter, a mercury-free fluorescent lamp (rare gas lamp) can be manufactured by forming an external electrode.

In addition, the phosphor of the present invention can be obtained by spreading a raw solution of a complex or a mixed solution of a raw material and a resin on various substrates, or after infiltrating into a microporous or mesoporous material such as zeolite or MCM-41. By distilling off the solvent and drying, it can be deposited on the surface of the pores to form a thin film. It is also possible for a complex to be present in the laminated structure of clay mineral or LB film. The fine metal complex can be dispersed in a non-soluble solvent, and then a thin film or a thick film can be produced by a spin coater, applicator, screen printing or the like. Thus, since the light-emitting body of the present invention is made of an organic material, the shape can be freely changed, and the light-emitting body can be introduced into various members.

The illuminant of the present invention is obtained by using at least one excitation source of visible light, ultraviolet light, vacuum ultraviolet light, light having a shorter wavelength than vacuum ultraviolet light, electron injection, electric field, heat, stress, ultrasonic waves, and radiation other than electromagnetic waves. Because it can emit light, ultraviolet light emitting elements such as three-wavelength fluorescent lamps, ultraviolet / visible light emitting elements such as LEDs, electron beam excited light emitting elements such as CRT, electron injection excited light emitting elements such as polymer LEDs and organic EL Also, it can be used for an excitation light emitting element by radiation other than electromagnetic waves such as a film batch.

Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
The following apparatus was used for identification of the obtained compound.
IR spectrum: FTIR-8200PC (manufactured by Shimadzu Corporation) (KBr tablet method: measurement of solid sample dispersed in KBr and pelletized), UV-vis spectrum: Hewlett
8453 Photo diode array spectrophotometer manufactured by Packard (a solid sample is dispersed in barium sulfate, placed on a sample substrate, and absorption is observed by reflection of light), ¹ H-NMR: JEOL
FT-NMR (solid sample dissolved in heavy solvent (deuterated chloroform) and measured), mass spectrum: JMS-700T Tandem MS-station mass spectrometer manufactured by JEOL, ESI-MS (Electro
Spray Ionization mass spectro), single crystal X-ray structural analysis: Rigaku Corporation RAXIS-RAPID imaging plate (Mounting a 0.2 mm square crystal on a glass fiber or capillary, and irradiating X-rays from the diffraction image , Structural analysis (teXsan) was performed), emission characteristics: measured using a fluorescence spectrometer (SPEX FLUOROLOG manufactured by JOBIN YVON).

Preparation of ligand 1,3,5-tris (2- (6-methyl-2-pyridinyl) ethyl) -2,4,6-triethylbenzene (Com-1) Put a rotor in a 100 mL two-necked reaction vessel A two-way cock and a septum cap were attached, the entire container was dried under reduced pressure, and the inside of the two-necked reaction container was kept under nitrogen. 2,6-Dimethylpyridine (1.60 g, 14.9 mol) and dehydrated THF (40 mL) were added and dissolved, and then the reaction system was cooled to −94 ° C. using an acetone bath using liquid nitrogen. N-Butyllithium (9.6 mL, 15.0 mmol) was then added. The color of the solution changed to reddish brown, and after leaving the cold acetone bath for about 3 hours, the color of the solution changed to dark reddish brown. This solution was again used at −94 ° C. using an acetone bath.
Then, a solution of 1,3,5-tris (bromomethyl) -2,4,6-triethylbenzene (2.0 g, 4.5 mmol) in dehydrated THF solution (40 mL) is slowly added in about 10 minutes. And dripped. After the dropwise addition, the solution was warmed to room temperature and stirred for 16 hours. Next, the reaction was terminated by opening the system, and the solvent was distilled off with an evaporator. To the obtained residue, 28% aqueous ammonia (10 mL) and methylene chloride (25 mL) were added and stirred for desalting, and then the methylene chloride layer was collected. The mixture was further extracted with chloroform (25 mL × 3). Concentrate with an evaporator and column chromatography (filler: alumina,
The origin component was removed with developing solvent: chloroform: hexane = 1: 2). Furthermore, the component of Rf = 0.18 was collected by column chromatography (filler: silica gel, developing solvent ethyl acetate: chloroform = 1: 1). When the solvent was distilled off with an evaporator and then dried under reduced pressure, the yield was 2.06 g and the yield was 87%, 1,3,5-tris (2- (6-methyl-2-pyridinyl) ethyl) -2,4, 6-Triethylbenzene was obtained.
As a result of identifying what was obtained, the following analytical values were obtained.
IR (KBr): 3060 (s, sp ₂ C—H), 2965, 2928, 2870 (s, sp ₃ C—H), 1590 (s), 1577 (s), 1455 (s), 1375 (m) cm ^-1
1 H-NMR (400 MHz, CDCl ₃ ) δ 1.21 (t, 9H, PhCH ₂ CH ₃ , J = 7.4 Hz), 2.58 (s, 9H, 6-CH ₃ -py) 2.74 (q , 6H, PhCH ₂ CH ₃ , J = 7.4 Hz), 294-3.01 (q, 12H, PhCH ₂ CH _2, J = 6.3 Hz), 6.92 (d, 3H, 3-H— py, J = 76 Hz), 7.00 (d, 3H, 5-H-py, J = 7.6 Hz), 7.49 (t, 3H, 4-H-py, J = 7.6 Hz)
ESI-MS (pos): m / z = 520.5 ((L + H) ⁺ ), calcd for C ₃₆ H ₄₆ N ₃

Preparation of ligand 1,3,5-tris (1-methyl-2-imidazolylethyl) -2,4,6-triethylbenzene (Com-2) A rotator was placed in a 100 mL two-necked reaction vessel and a two-way cock. And a septum cap were attached, the entire container was dried under reduced pressure, and the inside of the two-necked reaction container was kept under nitrogen. The two-necked reaction vessel was placed under nitrogen, dehydrated ethanol (8 mL), 1,2-dimethylimidazole (0.356 g, 3.42 mmol) and tetramethylethylenediamine (0.5 mL, 3.42 mmol) were added and stirred. The reaction system was cooled to −94 ° C. using liquid nitrogen and an acetone bath.
And n-butyllithium (2.43 mL, 3.42 mmol) was added. At this time, the solution turned yellow. After stirring for 1 hour, a solution prepared by dissolving 1,3,5-tris (bromomethyl) -2,4,6-triethylbenzene (0.505 g, 1.15 mmol) in dehydrated THF solution (4 mL) was slowly added in about 10 minutes. added. Further, it was washed with THF (4 mL) and added. The yellow solution gradually became cloudy. The cold acetone bath (−94 ° C.) was removed and warmed overnight at 40 ° C. using an oil bath. Thin layer chromatography: it was confirmed that progressed reaction (developing solvent: chloroform, detected by I ₂ method). n-Butyllithium was deactivated with distilled water (2 mL), evaporated to dryness with an evaporator, and dissolved in CH ₃ CN to remove an insoluble precipitate by suction filtration. And the obtained filtrate was concentrated with the evaporator. Ethyl ether was added and the mixture was allowed to stand for 1 hour, and then the ethyl ether layer was removed by decantation to remove components soluble in ethyl ether. Methylene chloride was added to the pale yellow oily substance obtained as a residue to elute components soluble in methylene chloride. The collected methylene chloride layer was dried with an evaporator, and the resulting pale yellow powder was collected to obtain 1,3,5-tris (1-methyl-2-indazolyl in a yield of 0.413 g and a yield of 74%. Ethyl) -2,4,6-triethylbenzene was obtained.
As a result of identifying what was obtained, the following analytical values were obtained.
IR (KBr): 2970 (s), 2934 (m), 2909 (m), 2872 (m, sp ₃ C—H), 1636 (s), 1529 (m), 1496 (s), 1462 (s) , 1415 (m), 1378 (m, C = C, C = N), 1283 (m) cm ^-1
1 H-NMR (400 MHz, CDCl ₃ ) δ 1.22 (t, 9H, PhCH ₂ CH ₃ , J = 6.96 Hz), 2.68 (q, 6H, PhCH ₂ CH ₃ , J = 7.56 Hz), _{2.87,3.11 (q, 12H, PhCH 2} CH 2, J = 8.68Hz), 3.51 (s, 9H, CH 3 -Im), 6.82,7.01 (d, 6H, 4,5-H-Im)
FAB-MS m / z
= 487.4 ((M + H) ⁺ ), 391.3 ((M-CH ₂ C ₄ N ₂ H ₅ ) ⁺ ), 96.1 ((C ₅ N ₂ H ₈ ))
HRMS
m / z = 487.3546 (487.3549 calcd for C 30 H 43 N 6)

Copper complexes composed of the ligands Com-1 and Com-2 and copper ions were obtained by a recrystallization method.

The emission luminance / spectrum of the transition metal complex was measured using a fluorescence spectrometer (SPEX FLUOROLOG manufactured by JOBIN YVON).

The obtained copper complex is applied onto an alumina substrate, placed in an evacuation system with two planar electrodes, and filled with a discharge gas (Xe 5% -Ne 95% mixed gas) to a constant pressure. A high-frequency voltage was applied to the planar electrode to discharge it, and light was emitted from the copper complex on the substrate to obtain a light emitting device.

Luminescent properties of copper complexes with Com-1 and chlorine as ligands:

(Fig. 4)
The fluorescence spectrum (reflection) was measured using a Shimazu UV2550 equipped with an integrating sphere on a sample in which a solid powder sample was attached to a filter paper. The phosphorescence spectrum of the solid sample was measured using a JASCO FP-6300 on the sample attached to the filter paper.
Luminescence characteristics: Luminescence characteristics as shown in FIG. 4 were obtained.

Claims (6)

A luminescent transition metal complex having a structure represented by the formula (1):

(1)
(In the formula (1), M is any of transition metal ions of Cu, Zn, Ag, Cd, Au, Hg, Pt, and Pd, and the coordinating group L ₁ or L ₂ is X or M. A heterocycle having a coordinated Y and Z, the heterocycle may or may not form a condensed ring structure, X is a halide ion or counter anion ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ^-
, CF ₃ SO ₃ ^— , B (C ₆ H ₅ ) ₄ ^— , but L ₁ and L ₂ are not both X. Y is an atom of N, S, P, or O. Z is —CR ³ ═CR ⁴ —, —N═CR ⁵ —, —NR ⁶ —, or —O—. Here, when L _n is X, there may be no linker coupled to L _n . R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom or an organic group having 1 to 20 carbon atoms. R ¹ is a hydrogen atom, a halogen atom or an organic group having 1 to 20 carbon atoms, and R ² is a hydrogen atom, a halogen atom or an organic group having 1 to 20 carbon atoms. When any of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ forms a condensed ring structure, ^{2 of} R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ Two or more may be connected to each other to form a ring. Linker is a linear or branched alkylene group having 1 to 20 carbon atoms, and one or two or more methylene groups in the alkylene group are -O-, -CO-,- Any one or more of O—CO—, —CH═CH—, —C≡C—, —N═N— may be substituted, and a hydrogen atom in the alkylene group may be substituted with a halogen atom; Also good. basement is a hydrocarbon group having 1 to 30 carbon atoms or a hetero compound residue containing 1 or more selected from the group consisting of N, S, P, and O, and having 1 to 30 carbon atoms. To express. T _n is an n organic group bonded to the basement, and is a linear or branched alkyl group having 1 to 20 carbon atoms, and the methylene group and the hydrogen atom in the alkyl group are the above linker It may be substituted in the same manner as in. n is an integer of 0 or more and 5 or less. When there are a plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, Y, Z, linker, and basement, these are independent of each other. ) The luminescent transition metal complex according to claim 1, wherein in the formula (1), basement is a 6-substituted benzene residue, linker is an alkylene group, and R ¹ is an alkyl group. The luminescent copper complex according to claim 2, wherein, in the formula (1), M is a bicoordinate copper ion. In the formula (1), the ethylene group of the linker is bonded to the 1, 3, 5 position of the benzene ring of the basement, and the ethyl group is bonded to the 2, 4, 6 position of the benzene ring of the basement, and L _n is monovalent. The luminescent copper complex according to claim 3, wherein a linker is bonded to the 2-position of the pyridine residue or 6-methylpyridine residue. 5. The luminescent copper complex according to claim 4, wherein, in the formula (1), either L ₁ or L ₂ is a chloride ion, and a linker is not bonded to L ₁ or L ₂ . A fluorescent light emitting device or a phosphorescent light emitting device comprising the light emitting transition metal complex according to any one of claims 1 to 5.