JPH0845715A - Organic magnetic body and time responsive organic magnetic body as well as manufacture thereof - Google Patents

Abstract

PURPOSE:To produce an organic magnetic body in increased magnetization and excellent reproducibility by a method wherein the organic magnetic body or time responsive organic magnetic body is cooled down to the temperature not exceeding a critical temperature to be held for a specific time within said magnetic body produced by dehydrogenating reaction of a precurcor having triarylmethane structure. CONSTITUTION:In an organic magnetic body produced by dehydrogenating reaction of a precurcor having triarylmethane structure represented by formula, the precurcor is cooled down to the temperature T1 not exceeding the critical temperature Tc to be held for a specific time, in the formula R<1>: substituted or unsubstituted condensated polycyclic arylene radical having at least two rings (provided hetero atoms comprising N, S or O may be contained in a ring member) or an electron donative radical substituted/phenylene radical, R<2>: substituted or unsubstituted aryle radical, n: degree of polymerization. Thereby an organic magnetic body in high magnetic susceptibility, and excellent reproducibility can be produced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic magnetic material having a high magnetic susceptibility, a time-responsive organic magnetic material and a method for producing them.

[0002]

2. Description of the Related Art Magnetic materials are widely used as permanent magnets, high magnetic permeability materials, and magnetostrictive materials in many fields such as acoustic materials, electric / electronic fields, automobile fields, medical fields, communication fields, and magnetic recording fields. Has been. In particular, organic magnetic materials have advantages over inorganic magnetic materials, such as lower density, better dispersibility in a binder resin, and many white or light-colored materials. Has been done.

For example, 1,4-bis (2,2 ', 6,6'-tetramethyl-1-oxyl) of Korshak et al.
A black powder polymer [Nature 326 370 obtained by heating or irradiating butane with ultraviolet rays.
(1987)], a black insoluble polymer obtained by polymerizing Torrance 1,3,5-triaminobenzene with iodine [Synth. Metal, 19 709 (198
7)], Polycarbene of Iwamura et al. (Chemical Society of Japan, 198
7, No. 4 595) and the like have been reported as organic ferromagnets. However, these are all difficult to synthesize, have problems with reproducibility, have problems with ferromagnetism, only a few percent of ferromagnetism develops, and the temperature of magnetism manifestation is extremely low. There were problems such as being unstable in the air.

Also, Otani et al. Use a condensed polycyclic aromatic resin (COPNA resin) made from a condensed polycyclic aromatic compound with p-xylene glycol as a linking agent, as an organic magnetic material in JP-A-62-521. It has been proposed in each of the publications of the same 62-522. Further, by using benzaldehyde or benzenedialdehyde in place of p-xylene glycol, a thermosetting resin having higher heat resistance can be obtained.
It was proposed in JP-A-2-2828080. It is said that ferromagnetism appears at room temperature, but the reproducibility was very poor because the polymer structure was not clearly understood.

[0005]

As described above, the reality is that an organic ferromagnetic material having good reproducibility has not been obtained yet. Therefore, an object of the present invention is to provide an organic magnetic material having a large magnetic susceptibility and excellent reproducibility and a method for manufacturing the same, and a time-responsive organic magnetic material capable of temporally controlling the magnetic susceptibility and a method for manufacturing the same. To provide.

[0006]

In order to achieve the above object, the inventors of the present invention have conducted extensive studies and as a result, have been able to obtain an organic paramagnetic substance with extremely good reproducibility, and have completed the present invention. It was That is, according to the present invention, an organic magnetic material or a time-responsive organic magnetic material obtained by dehydrogenating a precursor having a triarylmethane structure represented by the following general formula (1) has a critical temperature Tc or lower. Cool to temperature T ₁ ,
There is provided an organic magnetic material or a time-responsive organic magnetic material, which has a magnetic susceptibility increased by holding for a predetermined time.

Embedded image [In formula, R < ¹ >, R < ² > and n show the following, respectively. R ¹ : a substituted or unsubstituted fused polycyclic arylene group having two or more rings (provided that a ring member can contain a hetero atom consisting of N, S, or O) or an electron-donating group-substituted phenylene group, R ² : substituted Or an unsubstituted aryl group, n: degree of polymerization. ]

According to the present invention, the general formula (1)
In the organic magnetic material or the time-responsive organic magnetic material obtained by photodehydrogenation of the precursor having a triarylmethane structure represented by the above, the precursor contains a component having a molecular weight of less than 1,000. There is provided an organic magnetic material or a time-responsive organic magnetic material.

Further, according to the present invention, the general formula (1)
In the organic magnetic material or the time-responsive organic magnetic material obtained by photodehydrogenating a precursor having a triarylmethane structure represented by the following formula, in the photodehydrogenation reaction process, the molecular weight distribution of the precursor is high. There is provided an organic magnetic material or a time-responsive organic magnetic material, which is characterized by containing an increased component on the side.

Further, according to the present invention, the product obtained by the dehydrogenation reaction is subjected to a treatment for removing unreacted substances, and then the critical temperature T
A method for producing the organic magnetic material or the time-responsive organic magnetic material, which is characterized in that the magnetic susceptibility is increased by cooling to a temperature T _{1 of} c or less and holding for a predetermined time. , A temperature T ₁ is 200 K or less, and a method for producing an organic magnetic material or a time-responsive organic magnetic material is provided.

Furthermore, according to the present invention, in the above organic magnetic material or the above time responsive organic magnetic material, the radical concentration at the methine carbon site is at least 10 ¹⁷ / g.
The organic magnetic material or the time-responsive organic magnetic material is provided.

Further, according to the present invention, in the photodehydrogenation reaction, a solvent in which the fluorescence quantum yield of the precursor is 0.4 or less is used as a reaction solvent, In the method for producing the time-responsive organic magnetic material, in the photodehydrogenation reaction, the concentration of the precursor is set to 15% by weight or less. In the photodehydrogenation reaction, the manufacturing method further sets the wavelength range of irradiation light to 300 to
The method for producing the organic magnetic material or the time-responsive organic magnetic material, which has a thickness of 400 nm, is also an operation for removing a product from an unreacted material after completion of the reaction in the photodehydrogenation reaction and solidifying the product. The method for producing the organic magnetic material or the time-responsive organic magnetic material is provided, wherein the solidification operation of precipitating only the product using a poor solvent is performed only once.

The present invention will be described in detail below. A first invention of the present invention is an organic magnetic material or a time-responsive organic magnetic material obtained by dehydrogenating a precursor having a triarylmethane structure represented by the general formula (1),
The present invention relates to an organic magnetic material or a time-responsive organic magnetic material, which is obtained by increasing the magnetic susceptibility by cooling to a temperature T ₁ below a critical temperature Tc and holding it for a predetermined time, and a method for producing them. .

A second invention of the present invention is an organic magnetic material or a time-responsive organic magnetic material obtained by photodehydrogenation of a precursor having a triarylmethane structure represented by the general formula (1). Wherein the precursor has a molecular weight of 1,000
The present invention relates to an organic magnetic material or a time-responsive organic magnetic material characterized by containing less than the following components, and a method for producing them.

A third invention of the present invention is the above-mentioned general formula (1).
In the organic magnetic material or the time-responsive organic magnetic material obtained by photodehydrogenating a precursor having a triarylmethane structure represented by the following formula, in the photodehydrogenation reaction process, the molecular weight distribution of the precursor is high. The present invention relates to an organic magnetic material or a time-responsive organic magnetic material characterized by containing increased components on the side and a method for producing them.

For convenience of explanation, the second invention will be described below. Although the organic magnetic material of the present invention is paramagnetic, as shown in FIG. 3, at a low temperature of 200 K or less, the magnetic susceptibility is larger than that of the Curie law.
From 0 to 150K it is very noticeable. Further, it was found that by maintaining this temperature range, as shown in FIG. 7, the magnetic susceptibility has a time response of increasing with time.

That is, in the organic magnetic material obtained by photodehydrogenation of the precursor having the triarylmethane structure represented by the general formula (1), the precursor has a molecular weight of 1,
By containing less than 000 components, an organic magnetic material having extremely high reproducibility and high magnetic susceptibility can be obtained. The organic magnetic material is a time-responsive organic magnetic material whose magnetic susceptibility increases with time when kept in a predetermined temperature range.

For such an organic magnetic material, in the photodehydrogenation reaction, a solvent in which the fluorescence quantum yield of the precursor is 0.4 or less is used, and the concentration of the precursor is 15% by weight.
The following, the wavelength range of the irradiation light is 300 to 400n
m, or the separation and purification operation after the reaction,
The solidification operation in which only the product is precipitated using a poor solvent
It can be obtained with good reproducibility by performing only once.

The triarylmethane type resin before the photodehydrogenation reaction represented by the general formula (1) is a substituted or unsubstituted fused polycyclic aromatic compound having two or more rings or electron donation of benzene such as hydroxybenzene. It can be obtained by condensing and polymerizing a group derivative and a substituted or unsubstituted aromatic aldehyde in the presence of an acid catalyst. The triarylmethane type resin is subjected to a photodehydrogenation reaction to withdraw hydrogen of methine carbon to generate radicals and remove unreacted substances to obtain the organic magnetic material. Further, by keeping this in a predetermined temperature range, it becomes a time-responsive organic magnetic material whose magnetic susceptibility increases with time under a constant magnetic field.

The molecular weight of the triarylmethane type resin can be controlled by controlling the reaction temperature and the reaction time. So far, it has been considered that the presence of a low molecular weight component having a degree of polymerization n of 4 or less in a dehydrogenation reaction precursor impairs the stability of generated radicals due to its high mobility (JP-A-4-7316). Gazette). However, in the present invention, in the case of photodehydrogenation reaction, the molecular weight before light irradiation is 1,0
The low molecular weight component of less than 00 has a great influence on the increase of the radical concentration. That is, before and after light irradiation,
In addition to the dehydrogenation reaction, the precursor undergoes a structural change accompanied by a molecular weight change, and the structure of this final product contributes to the improvement of the radical concentration. A low molecular weight component having a molecular weight of less than 1,000 is indispensable for this structural change, and these components are hardly present after the reaction is completed. The content of these low molecular weight components having a molecular weight of less than 1,000 is preferably 10% or more,
% May be used.

The triarylmethane type resin is represented by the general formula (1), and R ¹ in the general formula is
Specific examples of R ² and R ² include the following. Specific examples of the bicyclic or more unsubstituted condensed polycyclic arylene group of R ¹ include naphthyl group, anthryl group, phenanthryl group, pyrenyl group, chrysene group, naphthacene group, benzophenanthryl group, perylene group, benzopyrenyl group. , A Koronene group, an acenaphthylene group, a decacyclene group and the like. Further, examples of the substituent include a hydroxyl group and a methyl group. In addition, N, S,
Heteroatoms such as O may be included. Further, the electron-donating group-substituted phenylene group is a phenylene group having a hydroxy group, a methoxy group, a methyl group, an ethyl group or the like as a substituent, and specific examples thereof include a phenol group and a resorcin group.

Further, specific examples of the unsubstituted aryl group of R ² include phenyl group and the like, and the substituent thereof is nitro group, methyl group, isopropyl group, t-butyl group, hydroxyl group, amino group. And so on. In addition, n means a polymerization degree and shows an integer of 1 or more.

Examples of the fused polycyclic aromatic compound applied when producing the triarylmethane type resin include naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, benzophenanthrene, perylene, benzopyrene and coronene. In addition to the benzene ring-fused type, there are 5-membered rings such as acenaphthylene and decacyclene, and the ring members may contain heteroatoms such as N, O and S such as tetrathiafulvalene. Among them, the reactivity can be increased by selecting a material having a relatively low melting point (250 ° C. or less) as a monomer and having a solubility in an organic solvent and an electron donating effect. In the case of a monocyclic aromatic compound, benzene may be used with 1 or 2 substituents of an electron donating group such as a hydroxy group, a lower alkoxy group and a lower alkyl group, and examples thereof include phenol and resorcin. However, they are not limited to these, and any of these may be used as a mixture.

As the substituted or unsubstituted aromatic aldehyde used as the linking agent, benzaldehyde is the most common, and nitro group, methyl group, isopropyl group, t
-Substituted product with butyl group, hydroxyl group, amino group, etc., for example, betylbenzaldehyde, nitrobenzaldehyde,
Examples thereof include, but are not limited to, benzenedialdehyde and the like. The molar ratio of the linking agent to the condensed polycyclic aromatic compound is preferably about 1 to 2.

Examples of the acid catalyst for the condensation reaction include various aromatic sulfonic acids such as p-toluene sulfonic acid, and strong acids such as fluoromethane sulfonic acid, hydrochloric acid, sulfuric acid and nitric acid. The addition amount of these is preferably 0.01 to 10% by weight with respect to the condensed polycyclic aromatic compound and the linking agent.

The condensation reaction is carried out in an inert atmosphere or in the air in the absence of a solvent at a temperature of about 100 to 150 ° C. for about 10 minutes to 6 hours. However, in the absence of a solvent, the reaction system may be cured in a short time, and in such a case, the reaction time can be extended by using a high boiling point solvent such as o-dichlorobenzene or nitrobenzene. .

Since the molecular weight distribution differs depending on these reaction conditions, the produced triarylmethane type resin has a low molecular weight component having a molecular weight of less than 1,000 measured by gel permeation chromatography (GPC). , It is confirmed whether or not they are contained, and if necessary, these components are added. Incidentally, these low molecular weight components, by controlling the reaction conditions,
It can be obtained in advance by a sorting operation using GPC.

Next, the photodehydrogenation reaction will be explained.
This is to carry out the dehydrogenation reaction by dissolving the precursor of the triarylmethane type resin in a reaction solvent and irradiating it with ultraviolet rays for about 30 minutes to 5 hours. Since the structure of the obtained product varies depending on the reaction conditions at this time, the reaction conditions for increasing the radical concentration with good reproducibility become important.

First, by using a reaction solvent having a fluorescent quantum yield of 0.4 or less, the stability of the generated radicals is improved. Examples of such a solvent include chloroform (fluorescent quantum yield of the above resin: 0.22), dichloromethane (0.38),
Halogen-based solvents such as carbon tetrachloride (less than 0.01) are typical, but not limited to. These may be used not only alone but also as a mixture. Also,
By setting the reaction concentration to 15% by weight or less, and further setting the wavelength of the irradiation light to 300 to 400 nm, the decomposition reaction that occurs as a side reaction is prevented. The irradiation light source is 300 to 400 such as various lasers, a combination of a high pressure or ultra high pressure mercury lamp and an appropriate filter.
The light is not particularly limited as long as it can be irradiated with light of nm. If necessary, a photosensitizer such as benzoquinone, benzophenone, or dicyanochlorobenzoquinone may be added as a catalyst to facilitate the reaction.

After the completion of the reaction, a poor solvent for the product is used to carry out a solidification operation for precipitating only the product, and the unreacted product is removed to isolate the product. At this time, the reprecipitation operation is indispensable in order to increase the radical concentration, but when it is repeatedly performed, the radical concentration is decreased conversely, so it is preferable to perform only once. Examples of the poor solvent used include alcohols such as methanol, ethanol, propanol, isopropanol, and cyclohexanol, aliphatic hydrocarbons such as hexane and octane, and alicyclic hydrocarbons such as cyclohexane, depending on products. However, the present invention is not limited to these.

The organic magnetic substance produced by the above photodehydrogenation reaction is paramagnetic, but its magnetic susceptibility is larger than the value derived from the Curie law at 200 K or less, and at 50 to 150 K, The magnetic susceptibility has a time responsiveness that increases with time, and there is a great possibility of practical application.

The spin concentration of the produced organic paramagnetic material is preferably 10 ¹⁷ spin / g. Especially 10 ¹⁹ spins /
It is preferably g or more, more preferably 10 ²⁰ spins / g or more.

Next, the third invention of the present invention will be described. As described above, the molecular weight of the triarylmethane type resin can be adjusted by controlling the reaction temperature and the reaction time. It has been reported so far that the molecular weight of the precursor is higher in the polymer region as an organic magnetic material (Japanese Patent Application Laid-Open No. 4-7316), and material development based on this idea has been advanced. We found a structural change accompanied by a change in the molecular weight distribution of the precursor in the reaction process, and confirmed that this structure contributes to the stabilization of radicals, the improvement of radical concentration, and the increase of magnetic susceptibility in a certain temperature range. It was That is, by adjusting the reaction conditions (reaction concentration, precursor molecular weight, etc.) so as to obtain a component that shifts the molecular weight distribution to the high molecular weight side in the photooxidation reaction process, not the molecular weight distribution of the precursor, the desired organic magnetic substance is obtained. And a time-responsive organic magnetic material can be obtained.

The organic magnetic material and the time-responsive organic magnetic material of the third invention use a solvent in which the fluorescence quantum yield of the precursor is 0.4 or less in the photodehydrogenation reaction. The concentration of the precursor is set to 15% by weight or less, the wavelength range of irradiation light is set to 300 to 400 nm, or the solidification operation of precipitating only the product by using a poor solvent in the separation and purification operation after the reaction is completed. It is the same as the case of the second invention that the reproducibility can be obtained by carrying out only once.

Next, the first invention of the present invention will be described. The precursor having the triarylmethane structure represented by the general formula (1) is subjected to dehydrogenation treatment and the unreacted material is removed to obtain a magnetic material. (The dehydrogenation treatment in this case is not limited to the photodehydrogenation method.) Although the product thus obtained is a paramagnetic substance, the present invention makes it possible to increase its magnetic susceptibility. . Usually, the magnetic susceptibility: χ obtained by subtracting the diamagnetic susceptibility of the molecule itself from the magnetic susceptibility of the organic paramagnetic substance can be expressed by the following equation (2).
(Curie rule) (In the formula, T: temperature, N: Avogadro's number, g: g value, M
B: Bohr particle, k: Boltzmann constant, S: spin quantum number) However, the organic paramagnetic product obtained by the above-mentioned production method is obtained by the formula (2) when cooled below the critical temperature: Tc. It was found that the value was larger than the theoretical value. Further, it was revealed that the magnetic susceptibility increases with the lapse of holding time in a certain temperature range of temperatures lower than Tc.

That is, it becomes possible to increase the magnetic susceptibility by holding the above-mentioned organic paramagnetic product at T ₁ for a predetermined time (T ₁ <Tc). T ₁ varies depending on the type of product, but is 200 K or less, particularly 50 to 150
A temperature range of K is preferred. Needless to say, T ₁ is not limited to a constant temperature, and various temperatures below Tc may be combined.

The spin concentration of the organic paramagnetic product is
As in the case of the second and third inventions, 10 ¹⁷ spin / g
The above is preferable. In particular, in order to increase both the original value of the magnetic susceptibility and the absolute value of the increasing magnetic susceptibility, the spin concentration is preferably 10 ¹⁹ spins / g or more, more preferably 10 ²⁰
Spin / g or more is preferable.

[0037]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 First, regarding the condensation reaction, 10.13 g (50 m) of pyrene was used.
mol), benzaldehyde (6.63 g, 60 mmo)
1) and 0.88 g (5% by weight) of p-toluenesulfonic acid were mixed, heated to 160 ° C. with a mantle heater, and reacted for 20 minutes. Then, the hardened reaction system was extracted with chloroform to dissolve soluble components, and reprecipitation operation was performed with methanol to obtain a triarylmethane type resin represented by the general formula (1) as a condensation product. Then, the molecular weight distribution of this resin in terms of standard polystyrene is determined by gel permeation chromatography (GPC Watt).
ERS) and the results are shown in FIG. From this result, it can be seen that this resin contains a sufficient amount of components having a molecular weight of less than 1,000.

Next, regarding the photodehydrogenation reaction, 100 mg of the above-mentioned triarylmethane type resin was dissolved in 600 ml of chloroform / carbon tetrachloride (1/1 vol), and a high pressure mercury lamp (Ushio UM-102) was placed under an Ar atmosphere. light as irradiation light through the _{(2 O240g / 1 CoSO 4 ·} 7H) filter and Pyrex glass cobalt sulfate aqueous solution,
After irradiation for 2 hours, 125 mg of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) was added, and light irradiation was continued for another 1.5 hours. Although the spectral transmittance of the irradiation light is shown in FIG. 2, it is mainly 300 to 400 n.
m light. After completion of the reaction, the reaction system was concentrated to about 5 to 10 ml, 20 times or more of methanol was added all at once to solidify, and the product was dried under reduced pressure to obtain a dehydrogenated product.

The magnetic properties of the obtained product were evaluated. First, a superconducting quantum interference type magnetization measuring device (S
Mod made by QUID Quantum Design
The temperature dependence of the magnetic susceptibility was determined using el MPMS-2) and is shown in FIG. The magnetic susceptibility values in the figure are obtained by subtracting the diamagnetic susceptibility values of the molecules themselves. Although an increase in magnetic susceptibility was observed with a decrease in temperature, in the case of a paramagnetic substance, normally, it should follow the Curie's law shown by the dotted line in the figure, but the magnetic substance of the present invention is more than this theoretical curve. It showed a large value, and it was remarkable especially at 50 to 150K.

Next, FIG. 4 shows the dependence of the magnetization on the magnetic field after holding this product at 90 K for 24 hours. However, in this case, the diamagnetic susceptibility of the molecule itself is also included. Since the magnetic field dependence of the magnetization is linear, it can be seen that this product is paramagnetic, but 10,000 G → -1
It was measured from 10,000G to 10,000G,
The values of magnetization are slightly different between the first 10,000 G and the last 10,000 G. This indicates that the magnetization of this material is increasing even within the measurement time. In addition, ESR spectrum (JEOL JEOL
-JES-TE300), the spin concentration was determined to be 1.5 x 10 ²⁰ spins / g.

Example 2 In Example 1, the temperature dependence of the magnetic susceptibility was measured for the product obtained by light irradiation for 3.5 hours without adding DDQ during the photodehydrogenation reaction. And shown in FIG. Similar to Example 1, an increase in magnetic susceptibility was recognized at low temperatures, and was particularly remarkable at 50 to 150K.

Example 3 10.13 g of pyrene was added to 20 ml of o-dichlorobenzene.
(50 mmol), benzaldehyde 6.63 g (60
mmol) and 0.88 g of p-toluenesulfonic acid
(5% by weight) was dissolved and heated under reflux at 150 ° C. for 2 hours, and then the hardened reaction system was extracted with chloroform to dissolve components, and reprecipitation operation was performed with methanol to obtain the above-mentioned general formula ( A triarylmethane type resin represented by 1) was obtained. Then, the molecular weight distribution of this resin in terms of standard polystyrene is determined by gel permeation chromatography (GPC
Waters) and shown in FIG.
From this result, it can be seen that this resin contains a sufficient amount of components having a molecular weight of less than 1,000. The photodehydrogenation reaction was carried out in the same manner as in Example 1 using this resin and using only chloroform as the reaction solvent.

As an evaluation of magnetic characteristics, the temperature dependence of magnetic susceptibility is shown in FIG. As in the case of Example 1, an increase in magnetic susceptibility was observed with a decrease in temperature, and the increase was 5
It was remarkable at 0 to 150K.

Example 4 10.13 g (50 mmol) of pyrene, 6.63 g (60 mmol) of benzaldehyde and 1.96 g (10% by weight) of p-toluenesulfonic acid were dissolved and dissolved at 115 ° C.
After reacting for 20 minutes in, the cured reaction system was extracted with chloroform to dissolve components, and reprecipitation operation was performed with methanol to obtain a triarylmethane type resin represented by the general formula (1). . Then, the molecular weight distribution of this resin in terms of standard polystyrene is measured by gel permeation chromatography (manufactured by GPC Waters),
It is shown in FIG. From this result, it can be seen that this resin contains a sufficient amount of components having a molecular weight of less than 1,000. The photodehydrogenation reaction was carried out in the same manner as in Example 1 using this resin and using chloroform / hydrogen tetrachloride (7/3 vol) as a reaction solvent.

As an evaluation of magnetic characteristics, the temperature dependence of magnetic susceptibility is shown in FIG. As in Example 1, an increase in magnetic susceptibility was observed as the temperature decreased, and the increase was 50%.
It was remarkable at ~ 150K.

Example 5 The product of Example 1 was kept at 90 K and the time dependence of magnetic susceptibility was measured. The results are shown in FIG. 7. As can be seen from these results, the magnetic susceptibility increased with the passage of time, and the increase did not reach saturation even after 760 minutes.

Comparative Example 1 Condensation reaction was carried out in the same manner as in Example 1, and the obtained resin was separated by GPC only for components having a molecular weight of 2,000 or more. This is subjected to a photodehydrogenation reaction in the same manner as in Example 1,
The temperature dependence of the magnetic susceptibility of the obtained product was measured, and the results are shown in FIG. When a low molecular weight component having a molecular weight of less than 1,000 was not contained, an increase in magnetic susceptibility was observed with a decrease in temperature, but 50 to 50, which was particularly remarkable in the examples.
The increase at 150 K was not so pronounced and the reproducibility was not good.

Comparative Example 2 A condensation product obtained in the same manner as in Comparative Example 1 and having a molecular weight of 2,000 or more was used, except that only benzene (fluorescent quantum yield 0.45) was used as a reaction solvent. Photodehydrogenation was carried out in the same manner as in Example 1, and the obtained product was
The temperature dependence of the magnetic susceptibility was measured and shown in FIG. In the reaction solvent with high fluorescence quantum yield, the increase in magnetic susceptibility was small at low temperature.

Comparative Example 3 1 g of a condensation product having a molecular weight of 2,000 or more obtained in the same manner as in Comparative Example 1 was added to chloroform / carbon tetrachloride (7 /
3) Dissolve in 600 ml, and as irradiation light, without applying a filter such as a cobalt sulfate aqueous solution or Pyrex glass to a high pressure mercury lamp, that is, 300 nm or less, and 400
In the same manner as in Example 1 without cutting off light of nm or more,
The photodehydrogenation reaction was performed, and the temperature dependency of the curing rate of the obtained product was measured and shown in FIG. When the concentration of photodehydrogenation reaction was high, the increase in magnetic susceptibility at low temperature was small.

Comparative Example 4 The condensation product having a molecular weight of 2,000 or more obtained in the same manner as in Comparative Example 1 was subjected to a photodehydrogenation reaction in the same manner as in Example 1, and after the reaction was completed, the product was solidified. At this time, the reaction solvent was directly concentrated to dryness without performing the reprecipitation operation to obtain a product, and the temperature dependence of the magnetic susceptibility was measured. The result is shown in FIG. The product had a small increase in magnetic susceptibility at low temperature unless solidification operation by precipitation treatment was performed.

Example 6 The triarylmethane type resin obtained in Example 1 was subjected to GPC.
The photooxidation reaction was performed according to the method described in Example 1 by using the precursor fractionated into the molecular weight distribution shown in FIG. 9, and the molecular weight distribution was measured as shown in FIG. When the dependence was measured, it was as shown in FIG. 11, and a time-dependent increase in magnetic susceptibility could be observed in the 50 to 150 K region. Also, the ESR spectrum in that temperature region is shown in FIG. 12, and the intensity was remarkably reduced as compared with the signal at room temperature.

Example 7 The triarylmethane type resin obtained in Example 1 was subjected to GPC.
According to the method described in Example 1, by using the precursor fractionated into the molecular weight distribution shown in FIG. 13, the molecular weight distribution was measured and the result was as shown in FIG. A time-dependent increase in magnetic susceptibility could be observed in the region.

Example 8 The triarylmethane type resin obtained in Example 1 was treated with GPC.
According to the method described in Example 1, by using the precursor fractionated into the molecular weight distribution shown in FIG. 15, the molecular weight distribution was measured and the result was as shown in FIG. A time-dependent increase in magnetic susceptibility could be observed in the region.

Comparative Example 5 Using the precursor described in Example 7, a photooxidation reaction was carried out at a reaction concentration as high as 10 times as described in Example 1, and the molecular weight distribution was measured. , No time-dependent increase in magnetic susceptibility could be observed (Fig. 1
8).

Comparative Example 6 The photo-oxidation reaction was carried out according to the method described in Example 1 except that the precursor described in Example 7 was used and the reaction solvent was benzene. The molecular weight distribution was as shown in FIG. No time-dependent increase in magnetic susceptibility could be observed.

Example 9 Pyrene (10.13 g) and benzaldehyde (6.63 g) were mixed with 0.88 g of paratoluenesulfonic acid and heated with stirring to maintain the system temperature at 160 ° C. After reacting for 20 minutes, it becomes viscous and eventually solidifies. After cooling to room temperature, the product was extracted with chloroform, purified by reprecipitation from methanol, collected by filtration, and dried under reduced pressure to obtain an initial condensate. Then, this condensate was dissolved in nitrobenzene at a concentration of 3.5 × 10 ^-2 mol / l and heated to 150 ° C. in an Ar atmosphere. Dichlorodicyanobenzoquinone (5.2 × 10 ^-2 mol)
It was added so as to have a concentration of 1 / l, and the reaction was allowed to proceed for 200 minutes (dehydrogenation treatment).

The solution was cooled to room temperature, purified by reprecipitation from methanol, filtered and dried under reduced pressure. The magnetic properties of this product are as follows: Superconducting Quantum Interferometry Magnetometer (SQUID; Quantum design)
It was performed using Model MPMS-2) manufactured by the same company.

FIG. 20 shows the temperature dependence of the magnetic susceptibility (χ). The dotted line shows the theoretical curve according to Curie's law. Usually, in the case of a paramagnetic substance, the magnetic susceptibility changes like this theoretical curve.However, in the product of the present invention, spin causes some interaction by cooling to below a certain critical temperature. , Its magnetic susceptibility shows a value larger than the theoretical value. Where the critical temperature is 1
It will be around 60K. Further, the increase in magnetization is particularly remarkable at 50 to 150K. The value of χ is obtained by subtracting the diamagnetic susceptibility of the molecule itself.

Example 10 Example 9 except that the dehydrogenation treatment was carried out at 100 ° C.
The product was obtained in a similar manner to. The temperature dependence of the magnetic susceptibility of this product is shown in FIG. At 130 K or less, the magnetic susceptibility shows a value larger than the theoretical value.

Example 11 Example 9 except that the dehydrogenation treatment was carried out at 190 ° C.
The product was obtained in a similar manner to. The temperature dependence of the magnetic susceptibility of this product is shown in FIG. Below 160 K, the magnetic susceptibility shows a value larger than the theoretical value.

Example 12 A product was obtained in the same manner as in Example 9 except that N, N-dimethylformamide was used as the solvent for the dehydrogenation treatment. The temperature dependence of the magnetic susceptibility of this product is shown in FIG. The magnetic susceptibility shows a value larger than the theoretical value at 200 K or less, and the increase in magnetization particularly at 50 to 150 K is remarkable.

Example 13 A product was obtained in the same manner as in Example 9 except that o-dichlorobenzene was used as the solvent for the dehydrogenation treatment.
The temperature dependence of the magnetic susceptibility of this product is shown in FIG. 20
The magnetic susceptibility shows a value larger than the theoretical value at 0 K or less, especially 5
The increase in magnetization at 0-150K is significant.

Example 14 An initial condensate formed as in Example 9 was treated with chloroform:
5.5 × 10 ⁻⁴ mol / l in a solvent of carbon tetrachloride = 1: 1
And was irradiated with light for 120 minutes using a high pressure mercury lamp in an argon atmosphere. Subsequently, dichlorodicyanobenzoquinone was added in an amount of 1.5 equivalents to 1 unit of pyrene-benzaldehyde in the initial condensation product, and 1
Light irradiation was performed for 20 minutes. Subsequently, the product was purified by reprecipitation from methanol, filtered, and the product was dried under reduced pressure.

FIG. 25 shows the temperature dependence of the magnetic susceptibility of this product.
Shown in The magnetic susceptibility shows a value larger than the theoretical value at 200 K or less, and the increase in magnetization particularly at 50 to 150 K is remarkable. Moreover, the spin concentration was 1.5 × 10 ²⁰ spins / g as measured by electron resonance spectrum (ESR spectrum).
The ESR spectrum is 100 kHz magnetic field modulation E
SR spectrometer (made by JEOL Ltd .; JEOL-JES-TE3)
00) was used.

Example 15 A product formed in the same manner as in Example 9 was fixed at a temperature of 120 K and the time dependence of magnetic susceptibility was measured. The result is shown in FIG. 26 (the vertical axis represents the amount of increase in magnetic susceptibility). By cooling to 120K, the magnetic susceptibility increases with the passage of time, and the saturation phenomenon occurs after about 400 minutes.

Example 16 The same measurement as in Example 15 was carried out at 90K. The results are shown in Fig. 27. By cooling to 90K, the magnetic susceptibility becomes extremely large with the passage of time, and the magnetic susceptibility does not reach saturation even after 760 minutes. The result of measuring the magnetic field dependence of the magnetization M after holding this product at 90 K for 24 hours is shown in FIG. 28 (the value of M also includes the diamagnetic susceptibility of the molecule itself). → It was measured in the order of →, and the magnetic susceptibility at the end point slightly increased compared to the start point, which reflects that the magnetic susceptibility increased slightly even after holding for 24 hours. It has been confirmed from the sex measurement that it is not completely saturated in 24 hours). Further, since the magnetic field dependence of M is linear, it can be seen that the product is paramagnetic. That is, the magnetic susceptibility increases with time while maintaining paramagnetism.

Next, (90 at 256K and 90K
Immediately after setting to K, after 110 minutes and after 260 minutes, the result of ESR spectrum measurement is shown in FIG. 29 (irradiation microwave is about 9).
GHz). When cooled to 90 K, the magnetic susceptibility increases from the theoretical value (see Example 9), and when kept at 90 K, the magnetic susceptibility increases with the elapse of time. Only sharp absorption is visible. That is, it does not mean that the change from paramagnetism to ferromagnetism occurs, but it supports the fact that the magnetic susceptibility increases with the passage of time as paramagnetic.

Example 17 The same measurement as in Example 15 was carried out at 70K. Results are shown in FIG. By cooling to 70 K, the magnetic susceptibility became extremely large with the passage of time, and after 760 minutes, it became considerably saturated.

Example 18 The same measurement as in Example 15 was carried out at 50K. The results are shown in Fig. 31. When cooled to 50 K, the increase in magnetic susceptibility is particularly large with the lapse of time, and the saturation has not been reached even after 300 hours.

[0071]

Since the organic magnetic material and the time-responsive organic magnetic material of the present invention have the above-mentioned constitution, they have a very high magnetic susceptibility, are soluble in an organic solvent and are stable in the air. is there.

Further, since the method for producing an organic magnetic material and the time-responsive organic magnetic material of the present invention has the above-mentioned constitution, according to the present method, an organic magnetic material having a very high magnetic susceptibility (time-responsive) is obtained. It can be obtained with extremely good reproducibility.

[Brief description of drawings]

FIG. 1 is a graph showing the molecular weight distribution of the triarylmethane type resin obtained in Example 1.

FIG. 2 is a graph showing spectrally transmitted light of irradiation light used in the photodehydrogenation reaction of Example 1.

FIG. 3 is a graph showing the temperature dependence of the magnetic susceptibility of the products obtained in Examples 1 to 4.

FIG. 4 is a graph showing the magnetic field dependence of magnetization after holding the product obtained in Example 1 at 90K for 24 hours.

5 is a graph showing the molecular weight distribution of the triarylmethane type resin obtained in Example 3. FIG.

FIG. 6 is a graph showing the molecular weight distribution of the triarylmethane type resin obtained in Example 4.

FIG. 7 is a graph showing the time dependence of magnetic susceptibility in Example 5.

FIG. 8 is a graph showing the temperature dependence of the magnetic susceptibility of the products obtained in Comparative Examples 1 to 4.

FIG. 9 is a graph showing the molecular weight distribution of the GPC preparative precursor resin used in Example 6.

FIG. 10 is a graph showing the molecular weight distribution of the product obtained in Example 6.

FIG. 11 is a graph showing temperature dependence of magnetic susceptibility of the product obtained in Example 6.

FIG. 12 Room temperature and 90 K of the product obtained in Example 6
FIG. 3 is an ESR spectrum diagram of a solid in FIG.

FIG. 13 is a graph showing the molecular weight distribution of the GPC preparative precursor resin used in Example 7.

FIG. 14 is a graph showing the molecular weight distribution of the product obtained in Example 7.

FIG. 15 is a graph showing the molecular weight distribution of the GPC preparative precursor resin used in Example 8.

16 is a graph showing the molecular weight distribution of the product obtained in Example 8. FIG.

FIG. 17 is a graph showing the molecular weight distribution of the product obtained in Comparative Example 5.

FIG. 18 is a graph showing the temperature dependence of the magnetic susceptibility of the product obtained in Comparative Example 5.

FIG. 19 is a graph showing the molecular weight distribution of the product obtained in Comparative Example 6.

20 is a graph showing the temperature dependence of the magnetic susceptibility of the product obtained in Example 9. FIG.

FIG. 21 is a graph showing the temperature dependence of the magnetic susceptibility of the product obtained in Example 10.

22 is a graph showing the temperature dependence of the magnetic susceptibility of the product obtained in Example 11. FIG.

23 is a graph showing the temperature dependence of the magnetic susceptibility of the product obtained in Example 12. FIG.

FIG. 24 is a graph showing the temperature dependence of the magnetic susceptibility of the product obtained in Example 13.

25 is a graph showing the temperature dependence of the magnetic susceptibility of the product obtained in Example 14. FIG.

FIG. 26 is a graph showing the time dependence of the magnetic susceptibility of the product obtained in Example 15 at 120K.

FIG. 27 is a graph showing the time dependence of the magnetic susceptibility at 90 K in Example 16.

28 is a graph showing the magnetic field dependence of the magnetization after the product in Example 16 was kept at 90 K for 24 hours.

29 is an ESR spectrum diagram at 256 K and 90 K in Example 16. FIG.

FIG. 30 is a graph showing the time dependence of the magnetic susceptibility at 70 K in Example 17.

31 is a graph showing the time dependence of magnetic susceptibility at 50 K in Example 18. FIG.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masahiro Taniuchi 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.

Claims (13)

[Claims] 1. An organic magnetic material obtained by a dehydrogenation reaction of a precursor having a triarylmethane structure represented by the following general formula (1), cooled to a temperature T ₁ below a critical temperature Tc, and kept for a predetermined time. An organic magnetic material having a magnetic susceptibility increased by holding the magnetic material. Embedded image [In formula, R < ¹ >, R < ² > and n show the following, respectively. R ¹ : a substituted or unsubstituted fused polycyclic arylene group having two or more rings (provided that a ring member can contain a hetero atom consisting of N, S, or O) or an electron-donating group-substituted phenylene group, R ² : substituted Or an unsubstituted aryl group, n: degree of polymerization. ] 2. A time-responsive organic magnetic material obtained by dehydrogenating a precursor having a triarylmethane structure represented by the general formula (1), cooled to a temperature T ₁ below a critical temperature Tc, A time-responsive organic magnetic material having a magnetic susceptibility increased by holding for a predetermined time. 3. An organic magnetic material obtained by photodehydrogenating a precursor having a triarylmethane structure represented by the general formula (1), wherein the precursor has a molecular weight of 1,000.
An organic magnetic material containing less than the following components. 4. A time-responsive organic magnetic material comprising a product obtained by photodehydrogenating a precursor having a triarylmethane structure represented by the general formula (1), wherein the precursor has a molecular weight of 1. A time-responsive organic magnetic material containing less than 000 components. 5. An organic magnetic material obtained by photodehydrogenating a precursor having a triarylmethane structure represented by the general formula (1), wherein the molecular weight of the precursor is in the photodehydrogenation reaction step. An organic magnetic material characterized in that it contains a component whose distribution is increased on the polymer side. 6. A time-responsive organic magnetic material comprising a product obtained by photodehydrogenating a precursor having a triarylmethane structure represented by the general formula (1), in the photodehydrogenation reaction process. And a time-responsive organic magnetic material, wherein the precursor contains a component whose molecular weight distribution is increased on the polymer side. 7. The product obtained by the dehydrogenation reaction is subjected to an unreacted material removal treatment, cooled to a temperature T ₁ below a critical temperature Tc, and held for a predetermined time to increase the magnetic susceptibility. The method for producing the organic magnetic material according to claim 1 or the time-responsive organic magnetic material according to claim 2. 8. The method for producing an organic magnetic material or a time-responsive organic magnetic material according to claim 7, wherein the temperature T ₁ is 200 K or less. 9. The radical concentration at the methine carbon site of the organic magnetic material or the time-responsive organic magnetic material is at least 10 ¹⁷ / g. The organic magnetic material according to claim 1 or the time-responsive organic magnetic material according to any one of claims 2, 4 and 6. 10. The organic compound according to claim 3, wherein in the photodehydrogenation reaction, a solvent in which the fluorescence quantum yield of the precursor is 0.4 or less is used as a reaction solvent. A method for producing a magnetic material or the time-responsive organic magnetic material according to claim 4 or 6. 11. The organic magnetic material according to claim 3 or 5, wherein the concentration of the precursor is 15 wt% or less in the photodehydrogenation reaction.
Alternatively, the method for producing the time-responsive organic magnetic material according to claim 6. 12. The organic magnetic material according to claim 3 or 5, or the organic magnetic material according to claim 4 or 6, wherein the wavelength range of irradiation light is 300 to 400 nm in the photodehydrogenation reaction. A method for producing the time-responsive organic magnetic material described. 13. In the photodehydrogenation reaction, a product is removed from an unreacted product after completion of the reaction to solidify,
The solidification operation in which only the product is precipitated using a poor solvent
The method for producing the organic magnetic material according to claim 3 or 5, or the time-responsive organic magnetic material according to claim 4 or 6, which is performed only once.