JPH0774309B2 - Rare earth complex of chiral phthalocyanine derivative and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bis (substituted phthalocyanine) rare earth complex having molecular asymmetry, which can be used for a nonlinear optical element, an optical recording material, etc., and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Phthalocyanine metal complexes are known as the chemically most stable organic compounds and are widely used in many fields. For example, a phthalocyanine metal complex (1 in FIG. 1) has hitherto been used as a pigment industrial material such as a pigment and a deodorizing material. In recent years, phthalocyaninato
Oxytitanium (IV) was found to have photoconductivity, and is widely used as a photoconductor for copying machines. Furthermore, the phthalocyaninato oxytitanium and the phthalocyaninato oxyvanadium have extremely large third-order nonlinear optical susceptibility and are expected to be applied as materials for nonlinear optical elements, and other materials such as sensor materials and fuel cell materials. It is also used for research and development. In addition to these, phthalocyanine metal complexes can be used as model compounds of chlorophyll and heme, and are useful for elucidating the chemical behavior of proteins bound to chlorophyll and heme in vivo.

However, the phthalocyanine metal complex has a large π-electron system, and since it has a large intermolecular interaction, it easily associates with a high degree and is generally insoluble or hardly soluble in an organic solvent. Due to this high association property, solid phthalocyanine metal complexes have crystal polymorphism, which hinders applied research and basic research.

When a phthalocyanine metal complex molecule having a long-chain alkyl group introduced is used, the phthalocyanine ring is retained on the water surface and the long-chain alkyl group is oriented in the air by the so-called Langmuir-Blodgett film formation method. It is possible. However, such an orientation state has poor stability and cannot be fixed. In addition, it is virtually impossible to accumulate a large number of monolayers formed in this way.

For these reasons, in the application to the above-mentioned various materials, or in the chemical research of the material itself, the research is being conducted focusing on the association property of the phthalocyanine metal complex.

The present inventors have improved solubility in organic solvents by introducing a side chain at a specific position of a phthalocyanine metal complex (Chemistry Letters, 1988,
1359 to 1362), reducing the effective symmetry around metal ions (Chemistry Letters, 1992, 763-)
It has been clarified that the orientation of the phthalocyanine metal complex molecule can be controlled by the above method and has already applied for a patent (Japanese Patent Publication No. 2-55769 and Japanese Patent Publication No. 4-106159). Here, "effective symmetry" means circular dichroism spectrum.
Perturbations in the time-dependent wavefunctions reflected in the ktur
Is established by ignoring distortions that can be described in theory
Means symmetry.

Use of dibenzo (b, t) phthalocyaninatozinc (II) synthesized by the method described in Chemistry Letters, 1992, pages 763-766 and Japanese Patent Publication No. 4-106159. Enables organic molecular beam deposition (Organi
A well-oriented thin film can be formed on a sapphire substrate by the c Molecular Beam Deposition (OMBD) method (Japanese Patent Application No. 4-12160). The effective symmetry around the metal ion of a general phthalocyanine metal complex is D _4h and D _4d , whereas this dibenzo (b, t) phthalocyaninatozinc (II) is twice as shown in FIG. It has an axis of symmetry, and the effective symmetry around the metal ion is lower than D _2h and a general phthalocyanine metal complex. In addition to applying the OMBD method,
It is considered that this decrease in symmetry contributes to the formation of a well-oriented thin film. It should be noted that the above-mentioned D _4h, your D _4d
And D _2h are called Schoenfries' symbols, and both
_{Represents a} point group, D _4h is a symmetry that includes a square plane
Assuming an axis perpendicular to the plane (σ _h ), use this as the axis of symmetry
When rotated, rotate 360 degrees to see the same structure four times.
Is a point group of molecules that can and D _4d includes a specific axis of symmetry.
If the relationship between the substance and the image is obtained in the plane (σ _v ),
Rotate 360 degrees around the nominal axis to see the same structure four times
The point cloud of molecules that can

Although nonlinear optical susceptibility is a characteristic indicating suitability as a material for a nonlinear optical element, the oriented thin film exhibits a large third-order nonlinear optical susceptibility, and can be suitably used as a material for an organic nonlinear optical element. .

On the other hand, regarding the second-order nonlinear optical susceptibility, a substance having a second-order hyperpolarizability is advantageous. The second-order hyperpolarizability becomes maximum when the difference in dipole efficiency between the excited state and the ground state is large and the energy difference between the two is small (Journal of American. Chemical Society, 113, 7227-7232 (1991)). This condition is satisfied, for example, when both the π-type electron donor and the π-type electron acceptor are present in one molecule and a strong charge resonance type interaction is present.

The present inventors have also conducted research on a sandwich type rare earth complex of phthalocyanine, and found that bis (phthalocyanine) rare earth (III) complexes have two phthalocyanine rings with a distance of about 2.7 angstroms from each other.
It was found that they were arranged at a twisted position of 45 degrees (Chemical Physics Letters, Volume 160, 163-167 (1989); Chemical Physics Letters, 165).
Vol., 397-400 (1990); Chemical Physics Letters, 166, 605-608 (1990)). That is, this type of complex satisfies the above conditions and may have a large second-order nonlinear optical sensitivity.

[0011]

As described above, the phthalocyanine metal complex is a substance useful in various fields, and is particularly expected as a material for optical elements. The formation of an oriented thin film, which is indispensable when applied to an optical element, has been made possible by the use of dibenzo (b, t) phthalocyaninatozinc (II) according to the research conducted by the present inventors. This example suggests that the orientation of the phthalocyanine metal complex can be improved by reducing the effective symmetry around the metal ion. However, the effective symmetry around the metal ion of dibenzo (b, t) phthalocyaninatozinc (II) is D _2h , and a phthalocyanine metal complex having an effective symmetry lower than this is not known.

Further, the phthalocyanine derivative having an effective symmetry lower than D _4h must be separated and purified from a mixture of various phthalocyanine derivatives after synthesis, but in order to efficiently separate the desired derivative, first, Chromatography of the desired phthalocyanine derivative in the form of a metal complex
It is necessary to separate them by the method and then desorb the central metal ion to form a phthalocyanine ion. The phthalocyanine ions as they are cannot retain their solubilities, stability, chromatographic-suitable affinity with a stationary phase and the like. However, ions such as zinc (II), copper (II), and iron (II), which are common as central metal ions of phthalocyanine metal complexes, cannot be eliminated by ordinary acid treatment, and thus, phthalocyanine derivatives have not been efficiently used. Could not be separated.

Therefore, an object of the present invention is to provide a rare earth complex of a phthalocyanine derivative having a molecular asymmetry (that is, a chiral) having a lower effective symmetry around a metal ion.

Another object of the present invention is to provide a method for efficiently producing a rare earth complex of a phthalocyanine derivative having the above-mentioned molecular asymmetry.

[0015]

Means and Actions for Solving the Problems As a result of intensive studies in view of the above circumstances, the present inventors have found that the four-fold effective symmetry (D _4h ) of ordinary phthalocyanine is changed to the two-fold effective symmetry (D _2h ). Using substituted phthalocyanine reduced below,
In a sandwich type complex in which this is coordinated with a rare earth (III) ion sandwiched between them, it was found that symmetry disappears and molecular asymmetry occurs, and the present invention has been completed.

That is, the complex of the present invention is characterized in that it has two-fold effective symmetry and that two substituted phthalocyanine ions are coordinated so as to sandwich a rare earth (III) ion.

The method for producing the complex according to the present invention is
After the synthesized substituted phthalocyanine magnesium (II) complex is formed, the desired substituted phthalocyanine-magnesium (II) complex is separated and purified, and the magnesium (II) ion is desorbed and substituted from the separated and purified complex. After obtaining a phthalocyanine ion and using the obtained substituted phthalocyanine ion as a dilithium salt, rare earth (III)
It is characterized by reacting with ions.

The present invention will be described in detail below.

Examples of the substituted phthalocyanine ion having a symmetry less than or equal to the two-fold effective symmetry which constitutes the complex of the present invention include the ions shown by 2 to 8 in FIG. In addition, in FIG. 1, M represents a metal ion.

Rare earth (III) ions are a group of trivalent cations with various ionic radii. The rare earth (III) ion used in the present invention is not particularly limited, but one having a large ionic radius is not preferable because the interaction between two π-π type phthalocyanineate / ions is small. Lutetium (III) ion can be used particularly preferably because it has the smallest ionic radius.
In addition, rare earth (III) ions that can be preferably used in the complex of the present invention include ytterbium (II
Examples thereof include I) ion and samarium (III) ion.

The structural formula of the complex according to the invention using a dibenzo (b, t) phthalocyanine ion as the substituted phthalocyanine ion is given by
The rare earth (III) ions sandwiched between the ions are omitted and shown in FIG.

The above-mentioned complex in which two phthalocyanine ions are coordinated with a rare earth (III) ion sandwiched therebetween (see FIG. 1).
1) was not chiral because the phthalocyanine ion had D _4h symmetry. However, as shown in FIG. 2, dibenzo (b, t) phthalocyanine-
A complex in which a substituted phthalocyanine ion such as a tho ion is coordinated with a rare earth (III) ion sandwiched between the dibenzo (b, t) phthalocyanine ion has a symmetry D
It is _2h and is a so-called chiral that can be divided into a pair of optical antipodes (enantiomers). In the complex shown in FIG. 2, the transition dipole moments of two dibenzo (b, t) phthalocyanine ions are clockwise and counterclockwise with respect to each other.
Take a 45 ° twisted arrangement. In addition, the distance between two substituted phthalocyanine ions sandwiching a rare earth (III) ion is generally small, especially when the rare earth (III) ion is lutetium.
In the case of (III) ions, the distance is as small as 2.7 angstrom. Therefore, the complex of the present invention has a strong interaction of the charge resonance type and satisfies the above-mentioned condition for increasing the second-order nonlinear optical susceptibility.

The method of synthesizing the substituted phthalocyanine in the method for producing the complex of the present invention is described in the above-mentioned JP-A-4-106.
The method described in Japanese Patent No. 159, Chemistry Letters, 1992, pages 763 to 766, etc. can be preferably used.

However, the central metal ions of the substituted phthalocyanine complex synthesized by these methods, such as zinc (II), copper (II), and iron (II), can be eliminated by acid treatment with concentrated sulfuric acid. It is inconvenient because it cannot be done. Therefore, in the production method of the present invention, these central metal ions are replaced with magnesium (II) ions, and a magnesium (II) complex of substituted phthalocyanine is formed by the same method.

The formed magnesium (II) complex is suitable for commonly used separation methods such as chromatography, and the desired substituted phthalocyanine magnesium (II) complex is used.
The complex can be separated and purified.

The separated / purified magnesium (II) complex of the desired substituted phthalocyanine is then converted into a salt such as a dilithium salt in an organic solvent and then treated with an acid to give a substituted phthalocyanine ion.

Finally, a rare earth (III) complex of a chiral substituted phthalocyanine can be obtained by reacting the obtained substituted phthalocyanine ion or its dilithium salt with a rare earth (III) ion.

For example, magnesium (II) complex (MgP
When preparing a lutetium (III) complex (Pc ₂ Lu (III)) from c), first, a metal-free phthalocyanine or a dilithium salt of phthalocyanine (PcLi ₂ ) is prepared from a magnesium (II) complex. The metal-free phthalocyanine can be prepared by easily desorbing magnesium by mixing MgPc with dilute sulfuric acid and allowing it to stand at room temperature for 2 to 3 minutes. PcLi
₂ is organic solvent such as quinoline and PHF (dehydrated)
Add 4 to 6 equivalents of n-butyllithium to
By adding gPc and heating at about 250 ° C. for about 30 minutes, it can be obtained with a yield of almost 100%. Here, Pc
It is more desirable to prepare Li ₂ .

Next, in an organic solvent such as quinoline, metal-free phthalocyanine or PcLi ₂ was added with Lu.
Add (OAC) ₃ (Lu (III) acetate) and add it at approx.
Pc ₂ Lu (III) can be obtained by heating for about 30 minutes.

The resulting rare earth (III) complex of the chiral substituted phthalocyanine is further treated by a chromatographic method using an optically active chromatographic material as a stationary phase to obtain an S configuration or a pair of optical antipodes. The R configuration complexes can be separated from each other.
For example, Ceramospher Chical RV-1 (manufactured by Shiseido Co., Ltd.), Chira Spher (manufactured by E. Merck), etc. are used as the stationary phase, and a methanol solution is used as the eluent for separation. At this time, it is particularly preferable to add about 1% of NH ₂ NH ₂ H ₂ O.

[0031]

EXAMPLES Example 1 a) Synthesis of dibenzo (b, t) phthalocyaninato magnesium (II) 2,3-dicyanonaphthalene 1.00 g (0.0056 mol), orthophthalodinitrile 0.90 g (0.0070 mol), acetic acid Magnesium (II) tetrahydrate 0.75 g (0.0035 mol) and hydroquinone 0.35 g (0.0032 mol) were thoroughly rubbed in an agate mortar, put in a test tube and immersed in a metal bath set at 270 ° C for several minutes. It was made to react. After the reaction, the product was pulverized and dissolved in tetrahydrofuran as much as possible, and the insoluble portion was filtered off. Next, this filtrate was passed through a column packed with basic alumina to remove impurities, and the solution that flowed out was concentrated and then allowed to stand to obtain crystals.

The crystals obtained were filtered off, and first tetrahydrofuran / acetone-based solvent, and then tetrahydrofuran /
By recrystallizing from a toluene solvent and tetrahydrofuran, 49 mg of dibenzo (b, t) phthalocyaninatomagnesium (II) was obtained. The electronic absorption spectrum and the nuclear magnetic resonance spectrum of the obtained dibenzo (b, t) phthalocyaninato magnesium (II) are shown in FIG. 4 and FIG. 5, respectively.

It is also possible to dramatically improve the yield by fractionating each of the by-produced phthalocyanine derivative complexes by the fractionating liquid chromatography method.

Elemental analysis value: carbon 75.10%, hydrogen 3.85
%, Nitrogen 17.42% (theoretical value: carbon 75.05%, hydrogen 3.90
%, Nitrogen 17.36%) b) Synthesis of dibenzo (b, t) phthalocyanine 151 mg (2.4 × 10 ⁻⁴ mol) of dibenzo (b, t) phthalocyaninatomagnesium (II) obtained in the above a) was added to 13 ml of quinoline. Suspended in the suspension, added 47 mg (7.3 × 10 ^-4 mol) of n-butyl lithium to this suspension,
The mixture was stirred for 2 hours and 30 minutes while heating in a metal bath at 60 ° C.

After allowing to cool, 50 ml of methyl alcohol was added to the reaction solution.
Was added and dissolved, 10 ml of 3N sulfuric acid was further added, and insoluble crystals were separated by filtration. The crystals separated by filtration were washed with water, washed several times with methanol and then with 1000 ml of tetrahydrofuran, and then the insoluble crystals were washed with a small amount of tetrahydrofuran and dried to obtain dibenzo (b, t) phthalocyanine. . The yield was 86 mg.

C) Synthesis of bis [dibenzo (b, t) phthalocyaninato] rare earth (III) complex 86 mg (1.4 × 10 ⁻⁴ mol) of dibenzo (b, t) phthalocyanine obtained in the above b) was added to 10 ml of quinoline. 26 mg of n-butyl lithium (4.4 x 10
^-4 mol) was added and the mixture was stirred in a metal bath at 250 ° C. for 1 hour. Then lutetium acetate (II
I) A suspension of 27 mg (7.7 × 10 ^-5 mol) was added, and 2 hours later, lutetium acetate (II
I) A suspension prepared by suspending 10 mg (2.8 × 10 ⁻⁵ mol) of
Two hours later, a suspension of lutetium (III) acetate 8 mg (2.3 × 10 ^-5 mol) in quinoline 1.5 ml was added, and the reaction was allowed to stand for 1 hour while maintaining the temperature at 250 ° C. Was advanced. After allowing to cool, n-hexane 100 is added to the reaction solution.
Crystals precipitated by adding ml were filtered off, and tetrahydrofuran was added to the obtained crystals to dissolve them. Then, this solution was filtered, and the filtrate was concentrated to obtain 63 mg of crystals.

The crystals obtained were dissolved in a small amount of tetrahydrofuran and passed through a column packed with basic alumina to remove a trace amount of impurities. Then, the column effluent was concentrated and 0.05 ml of hydrazine hydrate was added to remove bis [dibenzo (b, t) phthalocyaninato] lutetium (III) .cation radicals present in trace amounts in the form of radical salts. It was recovered as a neutral complex. The yield was 54 mg.

The obtained neutral complex was treated with an optically active column.
It was resolved into complexes of R -configuration as well as S -configuration.

The electronic absorption spectrum of the obtained bis [dibenzo (b, t) phthalocyaninato] lutetium (III) is shown in FIG.

Example 2 Lutetium acetate used in step c) of Example 1
Ytterbium (III) acetate and samarium (III) chloride were used in place of (III), and the complex was prepared in the same manner as in Example 1. As a result, bis [dibenzo (b, t) phthalocyaninato] ytterbium (III)
And bis [dibenzo (b, t) phthalocyaninato] samarium (III) were obtained, respectively, both of which were chiral.

[0041]

INDUSTRIAL APPLICABILITY As described above, the complex of the present invention is a chiral complex having molecular asymmetry and can easily form a thin film with well-controlled orientation. Further, the complex of the present invention has a strong interaction of the charge resonance type, and has a high second-order nonlinear optical susceptibility in addition to the third-order nonlinear optical susceptibility. Therefore, it can be suitably used as a material for a nonlinear optical element.

Further, the complex of the present invention has the property of being easily converted into a radical type by laser irradiation and returning to a neutral non-radical type by a basic substance, which is also useful as an optical recording medium. Is.

Further, according to the method for producing a complex of the present invention, a desired substituted phthalocyanine can be efficiently separated and purified from a mixture of various synthesized substituted phthalocyanines, and a chiral substituted phthalocyanine which is a final product is obtained. The rare earth (III) complex can be easily obtained with a high yield.

[Brief description of drawings]

FIG. 1 is a diagram showing structures of various phthalocyaninato metal complexes.

FIG. 2 is a diagram showing a pair of structural formulas of a bis [dibenzo (b, t) phthalocyaninato] lutetium (III) complex having an S configuration and an R configuration, which is a specific example of the complex of the present invention.

FIG. 3 is a diagram showing a structural formula of conventionally obtained dibenzo (b, t) phthalocyaninatozinc (II) having D _2h symmetry.

FIG. 4 is a diagram showing an electronic absorption spectrum of dibenzo (b, t) phthalocyaninato magnesium (III) synthesized in an example of the present invention.

FIG. 5 is a diagram showing a nuclear magnetic resonance spectrum of dibenzo (b, t) phthalocyaninato magnesium (III) synthesized in the example of the present invention.

FIG. 6 Bis [dibenzo (b, t) phthalocyaninato] lutetium (III) produced in an embodiment of the invention.
The figure which shows the electronic absorption spectrum of a complex.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-4-106159 (JP, A) JP-A-2-55769 (JP, A) JP-A-3-206091 (JP, A) JP-A-5- 297427 (JP, A) CHEMICAL PHYSICS L ETTERS, 160 (2), 1989, 163-167

Claims (5)

[Claims] 1. A complex having molecular asymmetry in which two substituted phthalocyanine ions having a low symmetry of two times or less effective symmetry are coordinated with a rare earth (III) ion sandwiched therebetween. 2. The complex according to claim 1, which is a bis (dibenzophthalocyaninato) rare earth (III) complex. 3. The rare earth (III) ion is lutetium
The complex according to claim 2, which is a (III) ion, a ytterbium (III) ion, or a samarium (III) ion. 4. After forming a synthesized substituted phthalocyanine magnesium (II) complex, a desired substituted phthalocyanine-magnesium (II) complex is separated and purified, and magnesium (II) ion is separated from the separated and purified complex. 2. The method for producing a complex according to claim 1, wherein the substituted phthalocyanine ion is eliminated to obtain a substituted phthalocyanine ion, the substituted phthalocyanine ion is converted into a dilithium salt, and then reacted with a rare earth (III) ion. 5. The production method according to claim 4, wherein after the reaction with a rare earth (III) ion, the reaction is further divided into optical isomers.