JP6009957B2 - Organometallic complex - Google Patents

Description

The present invention relates to an organometallic complex. More specifically, the present invention relates to an organometallic complex that can be suitably used as a light-emitting material utilizing fluorescence.

An organometallic complex has attracted attention as a light emitting material utilizing fluorescence, for example. In recent years, light emitting materials using fluorescence have a wide range of uses such as dye lasers, fluorescent pigments, fluorescent dyes, fluorescent marking materials, fluorescent indicators, security inks, and sensors, and the demand for these materials is expanding.

As a conventional organometallic complex, the use of a specific structure having a heteroatom-containing ring as a ligand is disclosed (for example, see Patent Documents 1 to 6 and Non-Patent Document 1). Moreover, specific polyazole polynitrobenzene and the silver complex which is the coordination compound are disclosed (for example, refer nonpatent literature 2).

International Publication No. 02/078343 JP 2000-252067 A JP 2000-302754 A Japanese Patent Application Laid-Open No. 11-144872 JP 2001-271063 A JP 2001-40346 A

“Soviet Journal of Coordination Chemistry”, 1990, No. 16, p. 876-880 “Chemical Communications”, 2009, Vol. 40, p. 6014-6016

The organometallic complex is composed of a ligand and a central metal atom, and by selecting each of them, an electron orbit or the like can be designed according to the purpose, and its function can be suitably expressed. As described above, in recent years, organic metal complexes are expected to be used in a wide range of applications such as dye lasers, fluorescent pigments, fluorescent dyes, fluorescent marking materials, fluorescent indicators, security inks, and sensors as light emitting materials that utilize fluorescence. Yes. Increasing variations of organometallic complexes that are suitably used for such applications can broaden the scope of selection when the organometallic complexes are used for various purposes in the applications, and have great technical significance. is there.

Many organic compounds and metal complexes have been studied as luminescent materials, but it is difficult to achieve sufficient color purity and material stability, especially for those emitting blue to violet fluorescence. There are few, and further development is desired.

The present invention has been made in view of the above-mentioned present situation, and is capable of emitting particularly blue to purple fluorescence with high color purity while ensuring sufficient stability as a complex. It is an object to provide an organometallic complex that can be suitably used as a material or the like.

The inventors of the present invention have studied various compounds that can be suitably used as a light emitting material utilizing fluorescence, and have focused on organometallic complexes. In particular, attention was paid to organometallic complexes using chelate ligands having a structure in which a ring having a nitrogen atom as a ring constituent atom is bonded to a carbon atom adjacent to a carbon atom directly bonded to an oxygen atom in a phenol ring. Many of such organometallic complexes have the property of emitting fluorescence. Then, the type of the central metal atom is specified, and in the chelate ligand, the position of the nitrogen atom in the ring having a nitrogen atom is specified, or the substituents of the ring having a nitrogen atom are combined to form a ring structure. The band gap between the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) can be expanded sufficiently by further specifying the structure of the ring having a nitrogen atom, etc. As a fluorescent light-emitting material, etc., it has been found that the color purity of light emission can be improved and the stability of the complex can be sufficiently improved, and the above problem can be solved brilliantly. In addition, the present inventors have found that hydrogen atoms bonded to such a ligand skeleton can be substituted with other atoms or atomic groups, thereby producing organometallic compounds having various structures. It has been reached.

That is, the present invention is an organometallic complex represented by the following general formula (1).

^(Wherein, X 1 to X ³ are the same or different, monovalent substituent which may carbon atoms have, or at least one nitrogen atom ^.X 1 to X ³ representing a nitrogen atom Provided that X ¹ is a nitrogen atom, and X ² and X ³ are each a carbon atom which may have a monovalent substituent, and the central metal atom M has a periodicity. It represents a metal atom belonging to Group 1 to Group 3, Group 12, or Group 13. In the arrow from the nitrogen atom to the central metal atom M, the nitrogen atom is coordinated to the central metal atom M. N is 2 or 3. R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or a monovalent or divalent substituent, and any two of R ^{1 to} R ⁴ Represents a divalent substituent, and these may be bonded to each other to form a ring structure other than an aromatic ring.
The present invention is described in detail below.

In the present specification, coordinating means that the nitrogen atom acts on the central metal atom M in the same manner as the ligand and has a chemical influence.

The central metal atom M in the organometallic complex of the present invention preferably represents beryllium, magnesium, calcium, barium, scandium, zinc, aluminum or gallium. More preferably, the central metal atom M represents beryllium, magnesium, zinc, or aluminum. More preferably, the central metal atom M represents magnesium, zinc, or aluminum.

In the above-mentioned general formula (1) in the organometallic complex of the present invention, the monovalent substituent that X ^{1 to} X ³ may have and the monovalent substituent in R ^{1 to} R ⁴ are halogen atoms. A hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 12 carbon atoms, a hetero atom-containing cyclic group having 0 to 12 carbon atoms, a cyano group, an alkoxy group having 1 to 12 carbon atoms, and 6 carbon atoms. It is preferable that it is a -12 aryloxy group, a C1-C12 alkylamino group, or a C6-C18 arylamino group. These monovalent substituents do not particularly contribute to material deterioration or performance deterioration. In addition, the carbon atom which may have a monovalent substituent in the above X ^{1 to} X ³ may have a hydrogen atom or may have a monovalent substituent. Say. In addition, the hetero atom-containing ring group means a cyclic group containing a hetero atom which is an atom other than carbon and hydrogen as a ring constituent atom.

It is preferable that at least two of R ^{1 to} R ⁴ in the organometallic complex of the present invention represent a hydrogen atom. More preferably, at least three of R ^{1 to} R ⁴ represent a hydrogen atom. For example, R ² and R ³ are the same or different and each represents a monovalent substituent, R ¹ and R ⁴ each represent a hydrogen atom, R ² represents a monovalent substituent, R ¹ , R ^It is preferable that ³ and R ⁴ each represent a hydrogen atom, R ³ represents a monovalent substituent, and R ¹ , R ² and R ⁴ each represent a hydrogen atom. Particularly preferably, R ^{1 to} R ⁴ each represent a hydrogen atom.

The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
The hydrocarbon group having 1 to 20 carbon atoms is a straight chain having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, and octyl group. C2-C12 alkenyl groups such as vinyl, 1-propenyl, allyl, and styryl groups; C2-C12 such as ethynyl, 1-propynyl, and propargyl groups An alkynyl group; a cyclic alkyl group having 5 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group and a cycloheptyl group; and an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, an alkenyl group, an alkynyl group or the like It is done.

The hydrocarbon group having 1 to 20 carbon atoms is preferably 1 to 8 carbon atoms among those described above. More preferably, it is 1-6. More preferably, it is 1-4. Particularly preferred is 1.

The halogenated hydrocarbon group having 1 to 12 carbon atoms is a haloalkyl group having 1 to 12 carbon atoms such as a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group; an aryl having 6 to 12 carbon atoms substituted with a halogen atom Groups.
The halogenated hydrocarbon group having 1 to 12 carbon atoms is preferably 1 to 8 carbon atoms among those described above. More preferably, it is 1-6.

The hetero atom-containing cyclic group having 0 to 12 carbon atoms is a 5-membered nitrogen-containing cyclic group such as pentazole; triazole, tetrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, pyrazole, pyrrole, pyrrolidine, oxazoline, furan Preferred examples include 5-membered heterocyclic groups such as thiophene; and 6-membered heterocyclic groups such as pyridine, pyrazine, piperidine, morpholine, thiazine and the like. These heteroatom-containing ring groups may be substituted with a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, or an alkynyl group. The C 0-12 heteroatom-containing ring group is preferably composed of one ring structure, in other words, it does not constitute a plurality of ring structures.
The C 0-12 heteroatom-containing cyclic group preferably has 1-8 carbon atoms among those described above. More preferably, it is 1-6.

The alkoxy group having 1 to 12 carbon atoms is methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group A straight chain or branched chain such as is preferable.
It is preferable that the said C1-C12 alkoxy group is C1-C8 among what was mentioned above. More preferably, it is 1-6. More preferably, it is 1-3.

Examples of the aryloxy group having 6 to 12 carbon atoms include a phenyloxy group and a benzyloxy group. In the aryloxy group having 6 to 12 carbon atoms, for example, the aryl group portion of the aryloxy group may be substituted with a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, or the like.
Among the above-mentioned aryloxy groups having 6 to 12 carbon atoms, those having 6 to 10 carbon atoms are preferable. More preferably, it is 6-8. More preferably, it is 6.

Examples of the alkylamino group having 1 to 12 carbon atoms include monoalkylamino groups having 1 to 12 carbon atoms such as a methylamino group and an ethylamino group; and 2 carbon atoms such as a dimethylamino group, a diethylamino group, a pyrrolidinyl group, and a morpholinyl group. -12 acyclic or cyclic dialkylamino groups are preferred.
It is preferable that the said C1-C12 alkylamino group is C1-C8 among what was mentioned above. More preferably, it is 1-6. More preferably, it is 1-4.

Examples of the arylamino group having 6 to 18 carbon atoms include monoarylamino groups having 6 to 18 carbon atoms such as phenylamino group and benzylamino group; N-alkyl-N— such as N-methyl-N-phenylamino group. Preferred examples include arylamino groups; acyclic or cyclic diarylamino groups having 12 to 18 carbon atoms such as diphenylamino group, carbazolyl group, phenoxazinyl group, and phenothiazinyl group. The acyclic diarylamino group means a group having no ring structure other than an aromatic ring, and the cyclic diarylamino group means a group having a ring structure other than an aromatic ring. In the arylamino group having 6 to 18 carbon atoms, for example, the aryl group portion of the arylamino group may be substituted with a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, or the like.
Of the above-mentioned arylamino groups having 6 to 18 carbon atoms, those having 8 to 18 carbon atoms are preferable. More preferably, it is 12-18. More preferably, it is 12.

In addition, the monovalent substituent is an acyl group such as an acetyl group, a propionyl group or a butyryl group; an N, N-dialkylcarbamoyl group such as an N, N-dimethylcarbamoyl group or an N, N-diethylcarbamoyl group; a thioacetyl group Thiocarbonyl groups such as thiobenzoyl group and methoxythiocarbonyl group; dioxaborolanyl group, stannyl group, silyl group, ester group, formyl group, thioether group, epoxy group, isocyanate group, hydroxyl group, sulfo group, sulfonyl It may be a group, phosphoryl group, carboxyl group or the like.

The monovalent substituent may be substituted with a halogen atom, a hetero atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aromatic ring, or the like as long as the effects of the present invention can be exhibited. In addition, when the alkyl group, aryl group, heteroatom-containing ring group or the like is substituted and has a monovalent substituent (when the monovalent substituent further has a monovalent substituent), monovalent substitution There are no particular restrictions on the position or number of groups to which the group is bonded.

Among these, the monovalent substituent is preferably a hydrocarbon group having 1 to 12 carbon atoms or a halogenated hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group having 1 to 12 carbon atoms is more preferably the linear or branched alkyl group having 1 to 12 carbon atoms or the aryl group having 6 to 12 carbon atoms. The halogenated hydrocarbon group having 1 to 12 carbon atoms is more preferably the fluorinated hydrocarbon group having 1 to 12 carbon atoms. More preferably, it is a trifluoromethyl group.

In the organometallic complex represented by the general formula (1), any two of R ^{1 to} R ⁴ represent a divalent substituent, which are bonded to each other to form a ring structure other than an aromatic ring. It may be formed. That is, any two of R ^{1 to} R ⁴ are bonded to each other by a covalent bond and a divalent substituent that is also bonded to a carbon atom constituting the phenol ring shown in the general formula (1). It may represent. At this time, the two divalent substituents together with the carbon atom of the phenol ring to which the two divalent substituents are bonded form a ring structure other than the aromatic ring. Any ring structure other than the aromatic ring may be used as long as it does not have multiple bonds constituting a conjugated system with the phenol ring. With such a configuration, the organometallic complex of the present invention can emit blue fluorescence or the like with high color purity. Moreover, it is preferable that ring structures other than this aromatic ring are comprised only from a carbon atom. In other words, the ring structure other than the aromatic ring is preferably not a heteroatom-containing ring structure.

The ring structure other than the aromatic ring is preferably a 5- to 7-membered ring, for example. More preferably, it is a 6-membered ring. The atoms constituting the ring structure other than the aromatic ring are the same or different and have a hydrogen atom or a monovalent substituent. When the atoms constituting the ring structure other than the aromatic ring have a monovalent substituent, the preferred configuration of the monovalent substituent is the same as the preferred configuration of the monovalent substituent described above. Moreover, it is especially preferable that each atom constituting the ring structure other than the aromatic ring has a hydrogen atom.

The divalent substituent preferably corresponds to, for example, the above-described monovalent substituent having a hydrogen atom. That is, a structure in which one hydrogen atom is eliminated from one having a hydrogen atom as the monovalent substituent can be used. Such substituents also do not particularly contribute to material deterioration or performance deterioration.

Incidentally, it means that the substituent in the X ¹ to X ³ are the fact that a monovalent substituent, which not bonded each other substituents X ¹ to X ^3, do not form a condensed ring structure To do. Also it means the substituents X ¹ to X ^3, not bound and the substituents R ¹ to R ^4, that do not form a condensed ring structure. Furthermore, the organometallic complex represented by the general formula (1) is usually not bonded to another organometallic complex by a covalent bond via a substituent or the like. With such a configuration, the organometallic complex of the present invention can emit blue fluorescence or the like with high color purity.

Although the monovalent substituent and the divalent substituent in the organometallic complex of the present invention have been described in detail, the above X ^{1 to} X ³ are the same or different and are a carbon atom having a hydrogen atom or a carbon number. Representing a carbon atom having 1 to 4 linear or branched alkyl groups is one preferred form of the invention.

Moreover, it is another preferable embodiment of the present invention that at least one of the monovalent substituents in X ^{1 to} X ³ is an aryl group having 6 to 12 carbon atoms. More preferably, at least one of the monovalent substituents in X ^{1 to} X ³ is a phenyl group or a naphthyl group. By directly bonding an aromatic ring to a ring having a nitrogen atom of the metal complex of the present invention, as in the case where at least one of the monovalent substituents in X ^{1 to} X ³ is a phenyl group or a naphthyl group, The effect of the present invention can be exhibited, and the heat resistance can be remarkably improved. For example, it is preferable that at least one of the monovalent substituents in X ¹ and X ² is a phenyl group.

In the above general formula (1), n is a number of 2 or 3, and this number is usually determined by the valence of the metal atom. In other words, there are two or three ligands of the organometallic complex represented by the general formula (1). These may be the same or different, but are preferably the same. Further, n is preferably 2.

It is preferable that one or two of the above X ^{1 to} X ³ in the organometallic complex of the present invention represent a nitrogen atom. Among them, the above X ² represents a nitrogen atom, X ¹ and X ³ are carbon atoms optionally having a monovalent substituent, the above X ³ represents a nitrogen atom, and X ¹ and X ² are What is a carbon atom which may have a monovalent substituent, What said X ² and X ³ represent a nitrogen atom, and X ¹ is a carbon atom which may have a monovalent substituent Are preferred respectively.

In the organometallic complex represented by the general formula (1), X ¹ is preferably a carbon atom having a monovalent substituent R ⁵ , for example. R ⁵ represents a hydrogen atom or a monovalent substituent. In other words, the organometallic complex of the present invention is preferably represented by the following general formula (2).

^(Wherein, X 2, ^{X 3,} the central metal atom ^M, R 1 to R ⁴ are, ^X 2, ^{X 3} in the general formula (1), the central metal atom ^M, is the same as R 1 to R ^4. R ⁵ represents a hydrogen atom or a monovalent substituent.)

When R ⁵ represents a monovalent substituent, the preferred form of the monovalent substituent is the same as the preferred form of the monovalent substituent that X ¹ may have. It is one preferable embodiment of the present invention that R ⁵ represents a hydrogen atom.

The organometallic complex of the present invention can be synthesized by various commonly used techniques. The ligand according to the organometallic complex of the present invention can be produced, for example, via a compound in which the oxygen atom of the phenol ring of the ligand is alkoxylated (hereinafter also referred to as an alkoxy form).
The above alkoxy compound is, for example, an organic solvent such as a five-membered aromatic compound having a nitrogen atom as a ring-constituting atom and phenol in which hydrogen on the ortho-position carbon is substituted with a reactive group such as a halogen atom. It can be obtained by reacting in the presence of a catalyst in a solvent. Moreover, in the alkoxybenzene which has a substituent on the carbon of ortho position, it can also obtain by cyclizing a part of this substituent.

The ligand according to the organometallic complex of the present invention can be obtained by dealkylating an alkoxy group using various reaction reagents in the above alkoxy body. Moreover, in the phenol which has a substituent on the carbon of ortho position, it can also obtain by cyclizing a part of this substituent.
The organometallic complex of the present invention can be obtained by reacting the above ligand with a metal salt under neutral or basic conditions. However, the manufacturing method of the organometallic complex of this invention is not restrict | limited to this.

The organometallic complex of the present invention can be suitably used as a light emitting material utilizing fluorescence, for example. As a light emitting material using fluorescence, a dye laser, a fluorescent pigment, a fluorescent dye, a fluorescent marking material, a fluorescent indicator, a security ink, a sensor, and the like are particularly preferable.

For use as a light emitting material that emits blue to violet light, for example, in fluorescence spectroscopic analysis, the fluorescence emission wavelength is preferably in the range of 360 to 480 nm. The difference (band gap) between the energy level of the highest occupied orbital (HOMO) of the organometallic complex of the present invention and the energy level of the lowest unoccupied orbital (LUMO) of the organometallic complex of the present invention is 2. It is preferable that it is 6 eV or more. More preferably, it is 2.8 eV or more. The difference is preferably 4.0 eV or less.
The difference between the energy levels of HOMO and LUMO of the organometallic complex of the present invention can be evaluated by a method of measuring by ultraviolet-visible spectroscopy (UV-Vis).

The organometallic complex of the present invention is excellent in stability as a complex, and can emit, for example, blue fluorescence with high color purity, such as dye laser, fluorescent pigment, fluorescent dye, fluorescent marking material, fluorescent indicator, security It can be suitably used as a light emitting material utilizing fluorescence, such as ink and sensor.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Note that “%” means “mass%” unless otherwise specified. Further, in the present specification, “substitution” and “substituent” refer to substitution with an atom or atomic group other than a hydrogen atom, and a group having such substitution, respectively. Further, the “phenol ring” includes a phenol group in which a hydrogen atom is eliminated from its hydroxyl group.

Note that fluorescence is light emission from an excited singlet state. In general, when light or electric energy is applied to a substance, the electronic state changes from a state called a ground state to an excited state (this process is called excitation). There are two types of excited states, a singlet excited state and a triplet excited state. When light energy is applied to the organometallic compound of the present invention at room temperature, it is normally excited to a 100% singlet excited state. In the above-described uses of the present invention, it is considered that most of the uses utilize light emission obtained by adding light energy.

Various measurements on the compounds synthesized in the examples were performed as follows.
⁽¹ H-NMR measurement)
The sample was dissolved in deuterated chloroform or deuterated dimethyl sulfoxide containing tetramethylsilane and measured with a nuclear magnetic resonance apparatus (Gemini 2000, 400 MHz, manufactured by Varian).
(Fluorescence spectrum measurement)
The sample was used as a dilute solution of dimethylformamide, and the fluorescence spectrum was measured using a fluorescence spectrophotometer (F-7000, manufactured by Hitachi High-Technologies Corporation). The excitation wavelength was 350 nm, and the place where the emission intensity was maximum was the fluorescence wavelength (λmax).
(Measurement of thermal decomposition temperature)
About 5 mg of a sample (complex compound) was placed in an aluminum pan using a differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA6200, manufactured by Seiko Instruments Inc.) and measured as follows.
Measurement temperature range: room temperature to 500 ° C
Temperature increase rate: 10 ° C / min
In the obtained thermal decomposition curve, the place where the weight loss was observed rapidly was defined as the thermal decomposition temperature.

Example 1 2- (1H-1,2,4-triazol-1-yl) phenolato zinc (II)
1- (2-methoxyphenyl) -1H-1,2,4-triazole

1,2,4-tetrazole (27.6 g, 400 mmol), 2-iodoanisole (23.4 g, 100 mmol), copper (I) oxide (1.43 g, 10 mmol), cesium carbonate (39.1 g, 120 mmol). It was dissolved (suspended) in dehydrated DMF (100 ml) and reacted at 120 ° C. for 24 hours. After the reaction, the solid content was removed by Celite filtration. The filtrate was dissolved in chloroform (300 ml), washed with water and brine, the organic layer was collected and dried over sodium sulfate. Sodium sulfate was removed by filtration, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to obtain 3.5 g of the desired product (yield 20%). ¹ H-NMR (400 MHz, CDCl ₃ ): δ 3.90 (s, 3H), 7.07 (t, 2H), 7.34 (t, 1H), 7.75 (d, 1H), 8.05 (S, 1H), 8.72 (s, 1H)

2- (1H-1,2,4-triazol-1-yl) phenol

1- (2-methoxyphenyl) -1H-1,2,4-triazole (1.05 g, 6 mmol) was dissolved in dehydrated dichloromethane (12 ml) and cooled in a dry ice-acetone bath at −78 ° C. Boron tribromide (1.0 M dichloromethane solution, 12 ml, 12 mmol) was gently added dropwise thereto. Thereafter, the temperature was raised to room temperature and reacted for 24 hours. After the reaction, the reaction solution was ice-cooled and quenched by adding water. Dissolved in chloroform (200 ml) and washed with water, the organic layer was recovered and dried over sodium sulfate. Sodium sulfate was removed by filtration, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to obtain 0.8 g of the desired product (yield 83%). ¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 6.93 (t, 1H), 7.05 (d, 1H), 7.23 (t, 1H), 7.55 (d, 1H), 8 .14 (s, 1H), 8.93 (s, 1H), 10.55 (br, 1H)

Bis 2- (1H-1,2,4-triazol-1-yl) phenolato zinc (II)

2- (1H-1,2,4-triazol-1-yl) phenol (970 mg, 6 mmol) and zinc (II) chloride (490 mg, 3.6 mmol) were dissolved in methanol (15 ml) and stirred at room temperature for 10 minutes. did. Triethylamine (1.0 ml, 7.2 mmol) was added thereto and reacted for 24 hours. After the reaction, the precipitated solid was collected by filtration under reduced pressure and washed with methanol to obtain 810 mg (yield 70%) of the desired product. ¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 6.93 (br, 2H), 7.05 (br, 2H), 7.23 (br, 2H), 7.54 (br, 2H), 8 .14 (s, 2H), 8.94 (br, 2H)

Example 2 Bis 2- (1H-1,2,4-triazol-1-yl) phenolato magnesium (II)

2- (1H-1,2,4-triazol-1-yl) phenol (210 mg, 1.3 mmol) and magnesium (II) chloride hexahydrate (160 mg, 0.8 mmol) were dissolved in methanol (5 ml). And stirred for 10 minutes at room temperature. Triethylamine (0.22 ml, 1.6 mmol) was added thereto and reacted for 24 hours. After the reaction, the precipitated solid was collected by filtration under reduced pressure and washed with methanol to obtain 300 mg (yield 68%) of the desired product. ¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 6.28 (t, 2H), 6.30 (d, 2H), 6.88 (t, 2H), 7.44 (d, 2H), 7 .94 (s, 2H), 9.60 (s, 2H)

Example 3 Tris 2- (1H-1,2,4-triazol-1-yl) phenolatoaluminum (III)

2- (1H-1,2,4-triazol-1-yl) phenol (1.0 g, 6.2 mmol) and aluminum isopropoxide (420 mg, 2.1 mmol) were dissolved in dehydrated THF (12 ml). The reaction was allowed to reflux for a time. After 2 hours, the mixture was cooled to room temperature and further reacted at room temperature for 24 hours. After the reaction, the precipitated solid was collected by filtration under reduced pressure and washed with methanol to obtain 630 mg (yield 59%) of the desired product.

Example 4 2- (5-Phenyl-1H-1,2,4-triazol-1-yl) phenolato zinc (II)
1- (2-methoxyphenyl) -5-phenyl-1H-1,2,4-triazole

1- (2-methoxyphenyl) -1H-1,2,4-triazole (2.1 g, 12 mmol), lithium t-butoxide (1.44 g, 18 mmol), copper (I) iodide (0.23 g, 1 .2 mmol), 1,10-phenanthroline (0.22 g, 1.2 mmol), and iodobenzene (2.45 g, 12 mmol) were dissolved in dehydrated DMF (7 ml), stirred for 5 minutes, and reacted at 100 ° C. for 24 hours. It was. After the reaction, it was dissolved in chloroform (200 ml), washed with water, and the organic layer was collected and dried over sodium sulfate. Sodium sulfate was removed by filtration, and the residue was concentrated and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 3) to obtain 2.5 g (yield 83%) of the desired product. ¹ H-NMR (400 MHz, CDCl ₃ ): δ3.51 (s, 3H), 6.94 (d, 1H), 7.04 (t, 1H), 7.24-7.50 (m, 7H) , 8.10 (s, 1H)

2- (5-Phenyl-1H-1,2,4-triazol-1-yl) phenol

1- (2-methoxyphenyl) -5-phenyl-1H-1,2,4-triazole (2.5 g, 10 mmol) is dissolved in dehydrated dichloromethane (20 ml) and cooled in a dry ice-acetone bath at −78 ° C. did. Boron tribromide (1.0 M dichloromethane solution, 20 ml, 20 mmol) was gently added dropwise thereto. Thereafter, the temperature was raised to room temperature and reacted for 24 hours. After the reaction, the reaction solution was ice-cooled and quenched by adding water. Dissolved in chloroform (200 ml) and washed with water, the organic layer was recovered and dried over sodium sulfate. Sodium sulfate was removed by filtration, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to obtain 2 g (yield 85%) of the desired product. ¹ H-NMR (400 MHz, CDCl ₃ ): δ 6.75 (t, 1H), 6.88 (d, 1H), 7.13 (d, 1H), 7.27 (t, 1H), 7.36 (T, 2H), 7.42 (t, 1H), 7.52 (d, 1H), 8.17 (s, 1H), 8.24 (s, 1H)

Bis 2- (5-phenyl-1H-1,2,4-triazol-1-yl) phenolato zinc (II)

2- (5-Phenyl-1H-1,2,4-triazol-1-yl) phenol (1.5 g, 6.5 mmol) and zinc (II) acetate (700 mg, 3.9 mmol) in methanol (60 ml) Dissolved and refluxed for 3 hours. After the reaction, the reaction mixture was cooled, and the precipitated solid was collected by filtration and washed with methanol to obtain 1.0 g (yield 59%) of the desired product. ¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 6.93 (br, 2H), 7.33 (br, 12H), 7.46 (br, 2H), 7.59 (br, 2H), 8 .15 (s, 2H)

Example 5 2- (5-Phenyl-1H-tetrazol-1-yl) phenolato zinc (II)
1- (2-methoxyphenyl) -5-phenyl-1H-tetrazole

5-Phenyl-1H-tetrazole (1.46 g, 10 mmol), 2-methoxyphenylboronic acid (1.52 g, 10 mmol), and copper (I) oxide (72 mg, 0.5 mmol) were dissolved in dehydrated DMSO (40 ml). The reaction was carried out at 100 ° C. for 24 hours in the atmosphere. After the reaction, the solid matter was removed by Celite filtration, and the filtrate was dissolved in chloroform (200 ml), washed with water, and the organic layer was collected and dried over sodium sulfate. The sodium sulfate was removed by filtration and the filtrate was concentrated to obtain 1.5 g (yield 60%) of the desired product. ¹ H-NMR (400 MHz, CDCl ₃ ): δ 4.09 (s, 3H), 7.12 (t, 2H), 7.24-7.58 (m, 5H), 8.22-8.25 ( m, 2H)

2- (5-Phenyl-1H-tetrazol-1-yl) phenol

1- (2-methoxyphenyl) -5-phenyl-1H-tetrazole (1.51 g, 6 mmol) was dissolved in dehydrated dichloromethane (12 ml) and cooled in a dry ice-acetone bath at −78 ° C. Boron tribromide (1.0 M dichloromethane solution, 12 ml, 12 mmol) was gently added dropwise thereto. Thereafter, the temperature was raised to room temperature and reacted for 24 hours. After the reaction, the reaction solution was ice-cooled and quenched by adding water. Dissolved in chloroform (200 ml) and washed with water, the organic layer was recovered and dried over sodium sulfate. Sodium sulfate was removed by filtration, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 2) to obtain 1.3 g (yield 92%) of the desired product. ¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 7.01 (t, 1H), 7.13 (d, 1H), 7.45 (t, 1H), 7.54-7.59 (m, 4H), 8.01-8.12 (m, 2H), 10.52 (s, 1H)

Bis 2- (5-phenyl-1H-tetrazol-1-yl) phenolato zinc (II)

2- (5-Phenyl-1H-tetrazol-1-yl) phenol (400 mg, 1.7 mmol) and zinc (II) chloride (140 mg, 1.0 mmol) are dissolved in methanol (5 ml) and stirred at room temperature for 10 minutes. did. Triethylamine (0.28 ml, 2.0 mmol) was added thereto and reacted for 24 hours. After the reaction, the precipitated solid was collected by filtration under reduced pressure and washed with methanol to obtain 100 mg (yield 22%) of the desired product.

Example 6 Bis 2- (5-phenyl-1H-tetrazol-1-yl) phenolatomagnesium (II)

2- (5-Phenyl-1H-tetrazol-1-yl) phenol (400 mg, 1.7 mmol) and magnesium (II) chloride hexahydrate (200 mg, 1.0 mmol) were dissolved in methanol (5 ml), and room temperature. For 10 minutes. Triethylamine (0.28 ml, 2.0 mmol) was added thereto and reacted for 24 hours. After the reaction, the precipitated solid was collected by vacuum filtration and washed with methanol to obtain 100 mg (yield 24%) of the desired product. ¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 6.29 (br, 2H), 6.71 (br, 2H), 7.04 (br, 2H), 7.28 (br, 8H), 7 .52 (br, 6H), 8.06 (br, 4H).

Example 7 2- (4-Phenyl-1H-1,2,3-triazol-1-yl) phenolato zinc (II)
2- (4-Phenyl-1H-1,2,3-triazol-1-yl) phenol

2-Azidophenol (3.0 g, 22.2 mmol), phenylacetylene (3.7 ml, 33.3 mmol) and diisopropylethylamine (4.3 ml, 24.4 mmol) are dissolved in dehydrated acetonitrile (44 ml) and stirred at room temperature. While adding copper (I) iodide (423 mg, 2.2 mmol). After reacting overnight at room temperature, ethyl acetate was added, and the organic layer was washed in this order with an aqueous ammonium chloride solution, a saturated aqueous sodium bicarbonate solution, and saturated brine. The organic layer was dried over magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography to obtain 1.4 g (yield 27%) of the desired product. ¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.04 (t, 1H), 7.24 (t, 1H), 7.33 (t, 1H), 7.41 (t, 1H), 7.48 -7.51 (m, 3H), 7.92 (d, 2H), 8.31 (s, 1H), 9.91 (s, 1H)

2- (4-Phenyl-1H-1,2,3-triazol-1-yl) phenolato zinc (II)

2- (4-Phenyl-1H-1,2,3-triazol-1-yl) phenol (450 mg, 1.9 mmol) and zinc (II) chloride (129 mg, 0.95 mmol) were dissolved in methanol at room temperature. Triethylamine (260 μl, 1.9 mmol) was added and stirred at room temperature overnight. After the reaction, the precipitated solid was collected by filtration under reduced pressure and washed with methanol to obtain 218 mg (yield 43%) of the desired product. ¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 6.54 (s, 1H), 6.95 (s, 1H), 7.02 (s, 1H), 7.31-7.34 (m, 2H), 7.41-7.43 (m, 1H), 7.56 (d, 1H), 7.80 (s, 2H), 9.10 (s, 1H)

Example 8 2- (4- (tert-Butyl) -1H-1,2,3-triazol-1-yl) phenolato zinc (II)
2- (4- (tert-Butyl) -1H-1,2,3-triazol-1-yl) phenol

2-Azidophenol (5.4 g, 40.0 mmol), tert-butylacetylene (5.9 ml, 48.0 mmol), diisopropylethylamine (7.7 ml, 44.0 mmol) were dissolved in dehydrated THF (80 ml), and room temperature. With stirring, copper (I) iodide (761 mg, 4.0 mmol) was added. After reacting overnight at room temperature, ethyl acetate was added, and the organic layer was washed in this order with an aqueous ammonium chloride solution, a saturated aqueous sodium bicarbonate solution, and saturated brine. The organic layer was dried over magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography to obtain 3.0 g (yield 35%) of the desired product. ¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.44 (s, 9H), 6.99 (t, 1H), 7.18 (d, 1H), 7.28 (t, 1H), 7.40 (D, 1H), 7.82 (s, 1H), 10.11 (s, 1H)

2- (4- (tert-Butyl) -1H-1,2,3-triazol-1-yl) phenolato zinc (II)

2- (4- (tert-butyl) -1H-1,2,3-triazol-1-yl) phenol (3.0 g, 13.8 mmol), zinc (II) chloride (1.39 g, 6.9 mmol) Was dissolved in methanol, triethylamine (1.9 ml, 13.8 mmol) was added at room temperature, and the mixture was stirred at room temperature overnight. After the reaction, the precipitated solid was collected by vacuum filtration and washed with methanol to obtain 1.2 g (yield 35%) of the desired product. ¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.42 (s, 9H), 6.98 (t, 1H), 7.18 (d, 1H), 7.26 (t, 1H), 7.41 (D, 1H), 7.84 (s, 1H)

From the measurement results of the fluorescence spectrum (measurement of fluorescence emission wavelength), it was found that all of the organometallic complexes of Examples 1 to 7 can suitably emit blue to purple fluorescence.

From the measurement results of the thermal decomposition temperature, the organometallic complexes of Examples 1 and 4 all have sufficient heat resistance, but the phenyl group is replaced with the carbon atom at the 5-position of the triazole ring of the organometallic complex of the present invention. In the directly bonded Example 4, the decomposition temperature was 394 ° C., and it was shown that the heat resistance was markedly superior compared to Example 1 in which the decomposition temperature was 313 ° C. If at least one of the monovalent substituents in X ^{1 to} X ³ in the organometallic complex of the present invention is an aryl group, it can be said that the heat resistance can be remarkably improved.

From these measurement results, it was confirmed that the organometallic complexes of the examples are organometallic complexes that can be suitably used as a light-emitting material utilizing fluorescence. The organometallic complex of the present invention has the same structural characteristics as the organometallic complexes described in the examples, and has the same characteristics as the organometallic complexes described in the examples, and a light emitting material utilizing fluorescence Etc. can be suitably used.

Claims (2)

An organometallic complex represented by the following general formula (1):

(In formula, X < ¹ > -X < ³ > is the same or different, and represents the carbon atom which may have a C1-C20 hydrocarbon group as a monovalent substituent, or a nitrogen atom. X < ¹ >. one or two to X ³ represents a nitrogen atom. However, ^{X 1} is nitrogen atom, and the ^{X 2} and ^{X 3,} respectively, a monovalent substituent as a hydrocarbon group having 1 to 20 carbon atoms The central metal atom M represents beryllium, magnesium, calcium, barium, zinc, aluminum, or gallium , and the arrow from the nitrogen atom to the central metal atom M is Represents that the nitrogen atom is coordinated to the central metal atom M. n is 2 or 3. R ^{1 to} R ⁴ are the same or different and are a hydrogen atom , a halogen atom, or a carbon number of 1 to 20. Hydrocarbon group or halogenated carbon having 1 to 12 carbon atoms It represents a hydrogen group.) The organometallic complex according to claim 1, wherein the central metal atom M represents beryllium, magnesium, zinc, or aluminum.