JP4328856B2 - Two-photon absorption material - Google Patents

Description

  The present invention relates to a novel compound useful as a two-photon absorption material or the like, an application material thereof, and an apparatus using the material.

Conventionally, in two-photon absorption materials, compounds such as dye compounds such as rhodamine and coumarin, dithienothiophene derivatives and oligophenylene vinylene derivatives have been used. However, these have a small two-photon absorption cross section showing the two-photon absorption capacity per molecule, and the two-photon absorption cross-section when using a femtosecond pulse laser is 200 × 10 ^-50 cm ⁴ · s · molecule. Most are less than ⁻¹ · photon ⁻¹ (see Non-Patent Document 1, for example).

Further, although a two-photon absorption compound composed of a carbonyl compound represented by a specific chemical formula has been disclosed, a satisfactory two-photon absorption cross-sectional area has not been obtained (see, for example, Patent Document 1).

  When the two-photon absorption cross-sectional area of a compound is small, increasing the compound concentration is one option for improving the two-photon absorption characteristics as a material. However, the solubility of the compound is limited and no significant improvement in properties is possible. Further, increasing the concentration is not necessarily an effective method because there is a risk of adversely affecting other components in the two-photon absorption material. For example, in two-photon absorption photomolding, three-dimensional memory, etc., the curing ability of the polymer may be hindered or the fluorescence intensity may decrease due to concentration quenching. May affect organizational activities.

  Since the two-photon absorption cross-sectional area of the compound is small and its concentration cannot be increased, if the two-photon absorption characteristics as a material cannot be improved, the laser peak intensity must be remarkably increased. As a result, not only a large-scale laser device is required, but also high-intensity energy that is close to destroying the material is used, so that the material can easily deteriorate or even be destroyed.

  As an application of a compound having two-photon absorption characteristics, photodynamic therapy that destroys cancer tissue and the like in a living body by singlet oxygen (active oxygen) generated by two-photon absorption excitation and heat is expected. However, even in the case of photodynamic therapy, since it cannot be expected that the concentration of the two-photon absorption compound is excessively increased in vivo, a compound having a high two-photon absorption cross section is desired.

Furthermore, even in an up-conversion laser that operates with a compound excited by two-photon absorption of light having a wavelength longer than the emission wavelength, increasing the concentration of the compound may cause concentration quenching and may not improve characteristics.
JP2003-183213 By Stephen Kershaw, "Two-Photon Absorption" in "Characterization techniques and tabulations for organic nonlinear optical materials", ed. By Mark G. Kuzyk, Carl W. Dirk, chapter 7, pp.515-654, Mercel Dekker, Inc. New York, 1988

The present invention has been made in view of the current state of the prior art described above, and its main purpose is a novel compound that has a huge two-photon absorption cross-sectional area and can exhibit high two-photon absorption characteristics at a low concentration. And providing its use.

  As a result of conducting research while paying attention to the current state of the technology as described above, the present inventors have found that a new ethylene-based compound has a huge two-photon absorption cross section, and a two-photon absorption material at a low concentration. It has been found that it exhibits excellent characteristics.

  That is, the present invention provides a novel compound useful as the following two-photon absorption material, and applied materials and devices using the compound for various uses.

  1. An ethylene compound represented by the following general formula (1);

(Wherein R _{1 to} R ₈ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and R ₉ and R ₁₀ are the same. Or, differently, it represents a pyridyl group or a pyridinium base, and n represents an integer of 1 to 4.

2. Item 2. The ethylene compound according to Item 1, wherein R ₉ and R ₁₀ are the same or different and are a group represented by the following general formula (2) or a group represented by the following general formula (3).

(In the formula, R ₁₁ is an alkyl group having 1 to 3 carbon atoms, A ⁻ is RSO ₃ ⁻ (wherein R is CF ₃ , phenyl, tolyl, or an alkyl group having 1 to 3 carbon atoms) ), Halogen anion, tetraphenylboron anion (Ph ₄ B ⁻ ) or ClO ₄ ⁻ ).

3. In general formula (1),
(A) R ₁ , R ₄ , R ₅ and R ₈ are hydrogen atoms, and R ₂ , R ₃ , R ₆ and R ₇ are lower alkoxy groups;
(B) R ₁ , R ₄ , R ₆ and R ₇ are hydrogen atoms, and R ₂ , R ₃ , R ₅ and R ₈ are lower alkoxy groups;
(C) R ₂ , R ₃ , R ₅ and R ₈ are hydrogen atoms, and R ₁ , R ₄ , R ₆ and R ₇ are lower alkoxy groups;
Or (d) the ethylene compound according to item 1 or 2, wherein R ₂ , R ₃ , R ₆ and R ₇ are hydrogen atoms, and R ₁ , R ₄ , R ₅ and R ₈ are lower alkoxy groups .

  4). A two-photon absorption material comprising the compound according to any one of Items 1 to 3.

  5). A light limiting material comprising the compound according to any one of Items 1 to 3.

  6). A curable material for a photocurable resin for photomolding, comprising the compound according to any one of Items 1 to 3.

  7. A three-dimensional optical memory material comprising the compound according to any one of Items 1 to 3.

8). A fluorescent dye material for a scanning two-photon fluorescence microscope comprising the ethylene compound according to any one of Items 1 to 3, wherein R ₉ and R ₁₀ are pyridyl groups.

9. A light limiting device in which the light limiting material according to Item 5 is disposed between the light collecting device and the collimating device.

10. A two-photon absorption photomolding device equipped with a pulse laser generator, a pulse laser condensing device, a photocurable monomer container, and a mechanism for scanning a predetermined condensing position in the photocurable monomer with a laser beam. An optical molding apparatus, wherein the curable material according to item 6 is contained in a photocurable monomer.

11. A three-dimensional optical memory device comprising a pulse laser generator, a pulse laser condensing device, a three-dimensional optical memory material, a mechanism for scanning a predetermined condensing position of the memory material with a laser beam, and an optical readout device, The three-dimensional memory device, wherein the three-dimensional memory material is the ethylene compound according to any one of the above items 1 to 3, wherein R ₉ and R ₁₀ are pyridyl groups.

12 A pulse laser generator, a pulse laser condensing device, the three-dimensional optical memory material according to item 7, a mechanism for scanning a predetermined condensing position of the memory material with a laser beam, and a change in refractive index in the optical memory material are detected. A three-dimensional optical memory device equipped with a mechanism.

13. A two-photon fluorescence microscope equipped with a pulse laser generator, a pulse laser condensing device, a fluorescent dye material according to Item 8, a mechanism for scanning a predetermined condensing position of the fluorescent dye material with a laser beam, and a photodetection device .

14 An upconversion laser material comprising the ethylene compound according to any one of Items 1 to 3, wherein R ₉ and R ₁₀ are pyridyl groups.

  15. 15. An upconversion laser device comprising the material according to item 14 and an optical resonator.

  16. A two-photon absorption excitation method in which excitation by two-photon absorption is caused by irradiating the compound according to any one of the above items 1 to 3 with light having a wavelength longer than the linear absorption wavelength of the compound.

The ethylene-based compound of the present invention is a novel compound not described in any literature and is represented by the following general formula (1).

(Wherein R _{1 to} R ₈ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and R ₉ and R ₁₀ are the same. Or, differently, it represents a pyridyl group or a pyridinium base, and n represents an integer of 1 to 4.

  As the pyridyl group, a 4-pyridyl group represented by the following general formula (2) is preferable,

As pyridinium base, 4-pyridinium base represented by the following general formula (3)

(In the formula, R ₁₁ is an alkyl group having 1 to 3 carbon atoms, A ⁻ is RSO ₃ ⁻ (wherein R is CF ₃ , phenyl, tolyl, or an alkyl group having 1 to 3 carbon atoms) ), Halogen anions, tetraphenylboron anions (Ph ₄ B ⁻ ) or ClO ₄ ⁻ ).

In the general formula (1), the alkyl group having 1 to 12 carbon atoms in R _{1 to} R ₈ includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and n-propyl. And a linear or branched alkyl group such as n-pentyl. Among these, methyl, ethyl, n-propyl, isopropyl and the like, which are alkyl groups having 1 to 3 carbon atoms, are preferable.

Examples of the alkoxy group having 1 to 12 carbon atoms include linear or branched groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy group, and n-pentoxy group. A branched alkoxy group can be exemplified. Among them, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy group and the like, which are lower alkoxy groups having about 1 to 4 carbon atoms, are preferable.

In the general formula (3), R ₁₁ represents an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include linear or branched alkyl groups such as methyl, ethyl, n-propyl and isopropyl. Examples of the halogen anion represented by A ⁻ include F ⁻ , Cl ⁻ , Br ⁻ , I ^{− and the} like.

Preferred ethylene-based compounds include (i) R ₁ , R ₄ , R ₅ and R _{8 of the} compound represented by the general formula (1) are hydrogen atoms, and R ₂ , R ₃ , R ₆ and R ₇ are (B) a compound in which R ₁ , R ₄ , R ₆ and R ₇ are hydrogen atoms, and R ₂ , R ₃ , R ₅ and R ₈ are lower alkoxy groups; ₂ , R ₃ , R ₅ and R ₈ are hydrogen atoms and R ₁ , R ₄ , R ₆ and R ₇ are lower alkoxy groups; (D) R ₂ , R ₃ , R ₆ and R ₇ are Examples thereof include a compound that is a hydrogen atom, and R ₁ , R ₄ , R _5, and R ₈ are lower alkoxy groups.

  Specific examples of the compound represented by the general formula (1) include a compound represented by the following formula (4), a compound represented by the following formula (5), and the like.

The compound of the present invention represented by the general formula (1) can be synthesized, for example, as follows.

As the starting material for the first step , Y. Iwase, K. Kamada, K. Ohta, K. Kondo, J. Mater. Chem. 2003, 13, 1575-1581. A compound represented by the following general formula (6) obtained by a method similar to the above can be used.

(In the formula, R _{1 to} R ₄ are as described above, and Z ₁ and Z ₂ are the same or different and represent a halogen atom.)
Examples of the halogen atom represented by Z ₁ and Z ₂ include F, Cl, Br, I and the like. The halogen atom used as Z ₁ is a halogen atom having a lower electronegativity than the halogen atom used as Z _2. It is preferable. For example, when using Cl as Z ₂ is, Z ₁ is Br or I is preferable.

  In the first step, by oxidizing the halogenated methyl group of the compound represented by the general formula (6), the following general formula (7)

(Wherein R _{1 to} R ₄ and Z ₁ are as described above).

The oxidation conditions in the first step are not limited as long as the methyl halide group is oxidized to produce an aldehyde group, and can be performed by a known method. For example, it may be performed by Kornblum oxidation conditions, Sommetlet oxidation reaction, Hass-Bender oxidation reaction, or the like.

Preferable methods include a method of oxidizing the compound represented by the general formula (6) using a mixture of sodium hydrogen carbonate (NaHCO ₃ ) and N, N-dimethyl sulfoxide (DMSO) as an oxidizing agent. Yes (Kornblum oxidation conditions). In this case, DMSO can also serve as a solvent.

  The oxidizing agent may be used in an amount of, for example, about 0.5 to 20 times equivalent, preferably about 1 to 10 times equivalent to the compound represented by the general formula (6). The reaction temperature is preferably from about 0 ° C. to around the boiling point of DMSO, more preferably from about 20 to 110 ° C. The reaction time may be about 0.1 to 24 hours, and preferably about 2 to 6 hours.

  The compound represented by the general formula (7) obtained in the first step can be isolated and purified by usual separation means such as silica column chromatography and recrystallization, and can be used in the next step.

In addition, in the case where the compound represented by the general formula (1) is obtained with n = 1, the compound represented by the general formula (7) obtained in the first step may be used in the fourth step. .

Second Step In the second step, an alkene is obtained from the aldehyde compound represented by the general formula (7) obtained in the first step (converting the C = O bond of the aldehyde group into a C = C bond). The conditions for this reaction are not limited and can be carried out by a generally used method. For example, it can be performed by a Wittig reaction.

The reaction conditions for performing the Wittig reaction are not limited as long as the alkene is synthesized from the aldehyde compound represented by the general formula (7) (if the C = O bond of the aldehyde group is converted to a C = C bond). . For example, metal alkoxides represented by R′ONa, R′OK (R ′ is an alkyl group), etc. (for example, tC ₄ H ₉ OK, etc.), alkyl lithiums such as nC ₄ H ₉ Li, C ₆ H ₅ Li, etc. In the presence of
A Wittig reaction can be carried out by adding halogenated methyltriphenyl phosphorus such as (C ₆ H ₅ ) ₃ PCH ₃ Br as a Wittig reaction reagent.

  As a solvent, if it is a polar solvent which does not raise | generate reaction with the said reagent, it will not be limited, For example, ethers, such as tetrahydrofuran, alcohols, such as methanol and ethanol, can be used.

The strong base compound and the Wittig reaction reagent are each used in an amount of about 0.2 to 5 times equivalent, preferably about 1 to 3 equivalents, relative to the compound represented by the general formula (7). The reaction temperature is preferably from about −20 ° C. to around the boiling point of the solvent, and more preferably about −20 to 50 ° C. As reaction time, about 0.1 to 24 hours is mentioned, Preferably it is about 2 to 6 hours.

  By the second step, a compound represented by the following general formula (8) can be obtained.

(Wherein R _{1 to} R ₄ and Z ₁ are as described above). Further, the compound represented by the general formula (8) can be used in the third step as it is without isolation.

Third Step In the third step, an aldehyde group is introduced into the end of the vinyl group of the compound represented by the general formula (8) to obtain an aldehyde compound represented by the following general formula (9).

(In the formula, R _{1 to} R ₄ and Z ₁ are as described above.)
As a method for performing the third step, a usual method used for introducing an aldehyde group into the terminal of the vinyl group can be used. For example, it is preferable to use a mixture of phosphorus oxychloride (POCl ₃ ) and N, N-dimethylformamide (DMF) as the reaction reagent. In this case, DMF can also serve as a solvent. These reaction reagents are each used in an amount of about 0.2 to 5 equivalents, preferably about 1 to 3 molar equivalents, relative to the compound represented by the general formula (8).

The reaction temperature is preferably from around the melting point of DMF to about 20 ° C, more preferably about -20 to 10 ° C. The reaction time may be, for example, about 0.1 to 24 hours, and preferably about 2 to 6 hours.

The compound represented by the general formula (9) obtained in the third step can be isolated and purified by usual separation means such as silica column chromatography and recrystallization, and the next step (second step or second step). 4 steps).

As described above, by repeating the introduction of an aldehyde group into a vinyl group (for example, the third step) and the conversion of the introduced terminal aldehyde group into a vinyl group (for example, the second step) as appropriate, Compounds of n = 2 to 4 represented by formula (10) can be obtained.

(In the formula, R _{1 to} R ₄ and Z ₁ are as described above.)
Fourth Step In the fourth step, the aldehyde compound represented by the general formula (10) is converted into the following general formula (11):

(Wherein R _{5 to} R ₈ are as described above, Z ₃ is a halogen atom, and R ₁₂ is an alkyl group having 1 to 3 carbon atoms). By the following general formula (12)

(Wherein R _{1 to} R ₈ , Z ₁ , Z ₃ and n are as described above). The phosphate compound represented by the general formula (11) is described in Y. Iwase, K. Kamada, K. Ohta, K. Kondo, J. Mater. Chem. 2003, 13, 1575-1581. Or a similar method.

The conditions for performing the fourth step are not limited as long as the compound represented by the general formula (10) and the compound represented by the general formula (11) are coupled. For example, it can be performed using a Wittig reaction.

The Wittig reaction in the fourth step is, for example, a metal alkoxide (eg, tC ₄ H ₉ OK) such as R ″ ONa, R ″ OK (R ″ is an alkyl group), nC ₄ H ₉ Li, C ₆ By reacting the aldehyde compound represented by the general formula (10) with the phosphate compound represented by the general formula (11) in the presence of a strong base compound such as alkyl lithium such as H ₅ Li. It can be carried out.

  The solvent is not limited as long as it is a polar solvent that does not inhibit the Wittig reaction. For example, ethers such as tetrahydrofuran and alcohols such as methanol and ethanol can be used.

The phosphoric acid compound and the strong base compound represented by the general formula (11) are used in an amount of about 0.2 to 5 times, preferably about 1 to 3 equivalents, relative to the aldehyde compound represented by the general formula (10). It is preferable. The reaction temperature is preferably from about −20 ° C. to around the boiling point of the solvent, and more preferably about −20 to 50 ° C. The reaction time can be exemplified by about 0.1 to 24 hours, preferably about 2 to 6 hours.

The compound represented by the general formula (12) obtained in the fourth step can be isolated and purified by usual separation means such as silica column chromatography and recrystallization, and can be used in the next step.

In the fifth step, the fifth step, halogen atoms at both ends in the compound represented by the general formula (12) obtained in the fourth step are represented by the following formulae:

Among the compounds represented by the general formula (1), which is the target compound of the present invention, by replacing R ₉ and R ₁₀ with a pyridyl group. Obtainable.

The conditions for this reaction are not limited as long as a substitution reaction is performed, but preferably a Heck reaction may be performed. For example, it is preferable to use about 0.5 to 5 equivalents, preferably about 2 to 3 equivalents of vinylpyridine with respect to 1 mole of the compound represented by the general formula (12).

As the solvent, amine-based solvents such as ethylamine, diethylamine, and triethylamine can be used, and a mixed solvent of triethylamine ((C ₂ H ₅ ) ₃ N) and acetonitrile is preferable. When a mixed solvent is used, the volume ratio is, for example, about triethylamine: acetonitrile = 1: 10 to 1: 1, preferably about 1: 9 to 1: 2. The reaction temperature is preferably about 0 to 80 ° C, more preferably about 20 to 60 ° C. The reaction time may be about 1 to 72 hours, and preferably about 24 to 36 hours.

In this step, a catalyst can be further used to promote the Heck reaction. Examples of the catalyst include palladium (II) acetate (Pd (OAc) ₂ ), the following formula

Trioltoluylphosphine or the like represented by the formula (12) can be used, and preferably both compounds are about 0.01 to 0.1-fold equivalents to 1 mol of the compound represented by the general formula (12). May be added about 0.02 equivalents.

  The target compound of the present invention represented by the general formula (1) obtained in the fifth step can also be isolated and purified by usual separation means such as silica column chromatography and recrystallization. It can be used in the sixth step. Moreover, it can confirm that the obtained compound is a compound represented by General formula (1) by normal confirmation means, such as NMR and elemental analysis.

Among the compounds represented by the sixth step general formula (1), R ₉ or R ₁₀ is a pyridinium base, the compound represented by the general formula (1) obtained in the fifth step, It can be obtained by reacting a salt represented by the general formula R ₁₁ A or a combination of an acid represented by HA and a base represented by R ₁₁ —OH. The reaction conditions are not limited, and the reaction may be usually performed under conditions that allow quaternary salification of the pyridyl group.

R ₁₁ is an alkyl group having 1 to 3 carbon atoms as described above, and A is RSO ₃ ⁻ (
In the formula, R is CF ₃ , phenyl, tolyl or an alkyl group having 1 to 3 carbon atoms), a halogen anion, a tetraphenylboron anion (Ph ₄ B ⁻ ), or ClO ₄ ^— .

The solvent that can be used in this step is not limited as long as it does not inhibit quaternary chlorination of the compound represented by the general formula (1) with the acid R ₁₁ A. For example, methylene chloride, chloroform, carbon tetrachloride, etc. Halogenated hydrocarbons, ethers such as tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as hexane, and the like can be used.

The acid R ₁₁ A is about 0.5 to 5 equivalents, preferably 2 to 3 with respect to the compound represented by the general formula (1).
About an equivalent amount can be used. The reaction temperature can be exemplified by about 0 to 80 ° C, preferably 20 to 60 ° C.
It is about ℃. The reaction time may be about 0.1 to 24 hours, preferably about 1 to 3 hours.

Thus, among the compounds represented by the general formula (1) which is one of the target compounds of the present invention, a compound in which R ₉ and / or R ₁₀ is a pyridinium base is obtained. The obtained compound can be isolated and purified by ordinary separation means such as silica column chromatography, recrystallization and the like. Moreover, it can confirm by normal confirmation means, such as NMR and elemental analysis.

Use of the Two-Photon Absorbing Material of the Present Invention The ethylene-based compound of the present invention is used in a state dissolved in an organic solvent such as dimethyl sulfoxide and dimethylformamide in the same manner as the compound used in the aforementioned known two-photon absorbing material. Alternatively, it may be used by being doped into a polymer such as polymethacrylmethyl, or the compound itself may be used alone.

The solvent, concentration, measurement conditions of the two-photon extinction coefficient, etc. are described in detail in Example 1. As is clear from Table 1 below, the ethylene compound of the present invention represented by the general formula (1) is ,
A large two-photon absorption cross section is obtained in a wide wavelength range.

  The compound of the present invention absorbs light having a longer wavelength as compared with the excitation wavelength in the case of linear absorption, that is, one-photon absorption, and causes excitation by two-photon absorption. Therefore, by irradiating the compound with light having a wavelength longer than the linear absorption wavelength, excitation by two-photon absorption can be generated, and the excitation phenomenon can be used for various applications described later. can do.

  The novel ethylene-based compound of the present invention can be effectively used for various applications such as a two-photon absorption material, its application material, and an apparatus using the material, utilizing such characteristics.

For example, the compound of the present invention represented by the general formula (1) is effectively used as a light-limiting material in a light-limiting device, a photo-curing resin curing material, a three-dimensional optical memory material, etc. it can. In addition, the compound of the present invention can be effectively used for photodynamic therapy using singlet oxygen, heat, etc. generated by excitation of the compound of the present invention.

Among the compounds used in the present invention, among the compounds represented by the general formula (1), compounds in which R ₉ and R ₁₀ are pyridyl groups exhibit fluorescence, and other than the above-described uses, for example, scanning This is useful as a fluorescent dye material in a scanning two-photon fluorescence microscope. Moreover, the application as a three-dimensional memory material using the fluorescence is also possible. Furthermore, it can also be effectively used as an upconversion laser material utilizing the upconversion phenomenon.

  Hereinafter, various apparatuses using the two-photon absorption material according to the present invention will be described. However, the use of the two-photon absorption material according to the present invention is not limited to these apparatuses, and it goes without saying that excellent effects are exhibited in various other apparatuses. In order to simplify the explanation, only the main components are shown in the illustrated apparatus, but other known components (not shown) are used in a practical apparatus.

FIG. 1 is a schematic view showing an outline of an example of an optical limiting device using the two-photon absorption material according to the present invention as an optical limiting material.

The laser beam incident from the outside (from the left side in FIG. 1) is condensed by the condensing device 1 (lens, concave mirror, etc.), becomes extremely high light intensity in the light limiting material 2, and induces two-photon absorption. And absorbed. In contrast, weak light such as ordinary light passes through the light-limiting material as it is without inducing two-photon absorption, and is returned to the original optical path by the collimator 3 (lens, concave mirror, etc.). , Exit the device. Therefore, in this light limiting device, only strong light is blocked by the device, so that the photodetector on the emission side or the naked eye of the observer is protected from the laser beam.

FIG. 2 is a schematic view showing an outline of an example of an optical molding apparatus using the compound of the present invention according to the present invention as a curing material.

  The laser beam passes from the pulse laser generator 4 through the mirror 8 and is collected by the pulse laser condensing device 5 (such as an objective lens of a microscope). Becomes intense and induces two-photon absorption. By this two-photon absorption, a reaction intermediate is generated, the coexisting monomers are polymerized, and a polymer is formed only in the vicinity of the focal point. As a result, a three-dimensional structure having an arbitrary shape can be formed. When performing fine control of a laser beam, a minute three-dimensional structure can be formed.

  This stereolithography apparatus is provided with a mechanism for scanning a predetermined condensing position with a laser beam, and the movement of the laser beam focus in the monomer is such that the stage 7 supporting the photocurable monomer 6 is movable. In this case, when the mirror 8 is a fixed type and the stage 7 is a fixed type, the mirror 8 can be a movable type (galvano mirror or the like).

FIG. 3 is a schematic diagram showing an outline of an example of a three-dimensional memory device using the compound of the present invention as a three-dimensional optical memory material. This figure is an example of a three-dimensional memory device using the compound of the present invention as a three-dimensional optical memory material and utilizing its fluorescence.

In the apparatus of FIG. 3, the light from the pulse laser generator 4 is condensed by the pulse laser condensing device 5 through the dichroic mirror 10 and focused on a desired location in the three-dimensional optical memory material 9. At the focal point, fluorescence induced by two-photon absorption is emitted. When the laser light intensity is increased above a certain level, the two-photon absorption material 9 in the focal portion is destroyed, and fluorescence is not generated in that portion. By repeating the condensing operation controlled in this manner, a portion that generates fluorescence and a portion that does not generate fluorescence by laser irradiation can be formed three-dimensionally at an arbitrary location. Thus, three-dimensional recording of information becomes possible.

  Information is read out by irradiating a laser beam weaker than the breakdown intensity to the destructive part and the non-destructive part, thereby inducing fluorescence by two-photon absorption. And can be detected by an optical readout device such as the photodetector 11. Also in this case, the memory device includes a mechanism for scanning a desired condensing position with a laser beam. As the scanning mechanism, for example, the three-dimensional optical memory material 9 placed on the stage 7 is moved. Alternatively, the laser beam may be scanned using a movable mirror (such as a galvanometer mirror).

FIG. 4 is a schematic view showing an outline of an example of a three-dimensional optical memory device using a refractive index change generated after two-photon absorption of the compound of the present invention. In this optical memory device, at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2) can be used as the optical memory material.

In the apparatus of FIG. 4, the three-dimensional information recording method may be the same as that of the apparatus of FIG. That is, the light from the pulse laser generator 4 is condensed by the pulse laser condensing device 5 through the dichroic mirror 10 and focused on a desired location in the three-dimensional optical memory material 9. In the vicinity of the focal point, a refractive index change occurs in the two-photon absorbing material due to a reaction generated after two-photon absorption or due to thermal modification. By repeating the condensing operation controlled in this way, it is possible to form a portion having a three-dimensionally different refractive index at an arbitrary position. Thus, three-dimensional recording of information becomes possible.

  Information can be read out by detecting a change in the refractive index in the optical memory material 9 using the confocal optical microscope 13, for example. For example, the light from the light source for detection 14 is condensed by a condensing device (such as a lens) 15 and a portion recorded as a change in refractive index in the optical memory material 9 is irradiated. The irradiated light passes through the aperture 17 through the light collecting device (lens etc.) 5 and the light collecting device (lens etc.) 16, and is then condensed by the light collecting device (lens etc.) 18, and the photodetector 11. Is detected. A change in refractive index at the recording position can be detected as a change in the amount of light by the photodetector 11.

In this method, by installing the aperture 17 at a focal point (confocal) position corresponding to the focal point in the optical memory material 9, position resolution in the depth direction is generated, and three-dimensional recording can be read out. For example, by moving the stage 7 or moving the position of the aperture 17, the horizontal recording can be read by scanning in the horizontal direction two-dimensionally. Further, by moving the stage 7 in the depth direction, reading in the depth direction becomes possible.

FIG. 5 is a schematic view showing an outline of an example of a two-photon fluorescence microscope using the compound of the present invention represented by the general formula (1) as a fluorescent dye material.

  The light from the pulse laser generator 4 is condensed by the pulse laser condensing device 5 through the dichroic mirror 10 and focused in the two-photon absorption material 12, thereby causing fluorescence induced by two-photon absorption. Cause it to occur. The two-photon absorption material 12 placed on the stage 7 is scanned with a laser beam, the fluorescence intensity at each location is detected by a light detection device such as the photodetector 11, and the computer is based on the obtained positional information. A three-dimensional fluorescence image is obtained by plotting with.

  Also in this case, the two-photon fluorescence microscope includes a mechanism for scanning a desired condensing position with a laser beam. As the scanning mechanism, for example, the two-photon absorption material 12 placed on the stage 7 is used. May be moved, or the laser beam may be scanned using a movable mirror (galvano mirror or the like).

FIG. 6 is a schematic diagram showing an outline of an upconversion laser device using the compound of the present invention as an upconversion laser material. The apparatus includes, for example, at least the upconversion laser material 19 and the optical resonator 20 of the present invention. The type, form, and the like of the optical resonator are not limited as long as the optical resonator can close the light path or feed back the light.

As an optical resonator, for example, a combination of at least two members selected from the group consisting of a concave mirror and a plane mirror; a ring-type optical resonator in which the optical path is not a reciprocating shape but a ring shape; An optical resonator that is processed into a waveguide type and uses end face reflection thereof; a distributed feedback (DFB) type optical resonator in which a part of the waveguide is processed into a diffraction grating shape can be used.

  According to the up-conversion laser device of the present invention, for example, light is generated from the material for the up-conversion laser including the compound of the present invention that is excited by two-photons by irradiation with a laser beam (not shown) serving as an excitation source. It is fed back by the optical resonator and amplified when it repeatedly passes through the upconversion laser material, thereby causing a laser oscillation phenomenon, and the laser oscillation light can be taken out as appropriate.

  Since the novel compound of the present invention has a huge two-photon absorption cross section, it exhibits high two-photon absorption characteristics at a low concentration. Therefore, according to the present invention, not only a highly sensitive two-photon absorption material can be obtained, but there is no need to increase the intensity of light applied to the material, and deterioration or destruction of the material can be suppressed. The adverse effect on the properties of other components can also be reduced.

  Hereinafter, examples will be shown to further clarify the features of the present invention. The present invention is not limited to these examples.

Synthesis example 1
Following formula

A compound represented by: 1-bromo-2,5-dimethoxy-4-chloromethylbenzene (26.6 g, 0.10 mol) and NaHCO ₃ (42.0 g, 0.50 mol) are dissolved in DMSO (350 ml), The mixture was refluxed at 115 ° C. for 20 hours. After the reaction, the reaction mixture was cooled to room temperature and DMSO was removed by distillation under reduced pressure to obtain an orange-brown solid.

Water was added thereto, and the target compound was extracted with dichloromethane. After drying the organic layer with anhydrous MgSO ₄ , anhydrous MgSO ₄ was filtered through filter paper, and the filtrate was distilled off under reduced pressure to obtain a residue. The resulting residue was purified using a silica gel column chromatography method (developing solvent: chloroform) to obtain a yellow powder. Furthermore, it is recrystallized (hexane: ethyl acetate = 5: 1 = 600 ml) and is a yellow needle-like crystal, the following formula (13)

A compound represented by: 4-bromo-2,5-dimethoxybenzaldehyde was obtained. The yield was 18.2 g, and the yield was 74.3%.

Synthesis example 2
To THF (100 ml), t-BuOK (8.24 g, 73.4 mmol) and Methyltriphenylphosphonium bromide (21.9 g, 61.2 mmol) were added. Thereto was added dropwise the compound (13) synthesized in Synthesis Example 1 (15.0 g, 61.2 mmol) / THF (100 ml), followed by stirring for 1.5 hours. After the reaction, THF was removed by distillation under reduced pressure, water was added, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous MgSO ₄ , and then anhydrous MgSO ₄ was filtered through a filter paper.

A red brown oil compound represented by: 4-bromo-2,5-dimethoxyvinylbenzene was obtained. This compound was used in the next reaction without purification.

Synthesis example 3
POCl ₃ (13.2 g, 86.0 mmol) was added dropwise to DMF (34.3 g, 469.2 mmol) at 10 ° C. or lower. next,
The compound (14) (19.0 g, 78.2 mmol) / DMF (15 ml) obtained in Synthesis Example 2 was added dropwise at 10 ° C. or lower, left at room temperature for 1 hour, and further heated to reflux at 80 ° C. for 1 hour.

Thereafter, sodium acetate (81.6 g, 994.5 mmol) / H ₂ O (200 ml) was added dropwise while cooling in an ice bath. The reaction solution was heated to reflux at 75 ° C. for 15 minutes, cooled to room temperature, water was added, and the mixture was extracted with ether (750 ml). The organic layer was dried over anhydrous MgSO ₄ , then anhydrous MgSO ₄ was filtered through filter paper, and the filtrate was distilled off under reduced pressure to obtain a yellow solid. Furthermore, recrystallization with methanol (50 ml) gave the following formula (15)

A yellow powder compound represented by the formula: 1-bromo-2,5-dimethoxy-2-propenal or 1-bromo-2.5-dimethoxycinnamaldehyde was obtained. The yield was 3.15 g, and the yield was 14.9%.

Synthesis example 4
Under a nitrogen atmosphere, t-BuOK (0.671 g, 5.98 mmol) was added to THF (30 ml). In the reaction solution, the following formula (16)

1-bromo-2,5-dimethoxy-4- (diethoxyphosphorylmethylene) benzene (1.22 g, 3.32 mmol) was added, and compound (15) (0.90 g, 3.32 mmol) / THF (25 ml) ) Was added dropwise, followed by stirring for 1 hour. After 1 hour, the reaction solvent was distilled off under reduced pressure, and the resulting yellow powder was purified by a mixed recrystallization method using ethyl acetate: chloroform = 1: 1 (150 ml), and the following formula (17)

As a result, 1,4-bis (2,5-dimethoxy-4-bromophenyl) butadiene was obtained. The yield was 1.05 g, and the yield was 65.3%.

Synthesis example 5
Under a nitrogen atmosphere, triethylamine (130 ml) and acetonitrile (260 ml) are added to compound (17) (0.800 g, 1.65 mmol), and (O-tol) ₃ P (1.01 g, 3.30 mmol), 4-vinylpyridine ( 382.2 mg, 3.64 mmol) and Pd (OAc) ₂ (74.3 mg, 3.31 mmol) were added in this order, and the mixture was heated to reflux at 95 ° C. for 20 hours. After 20 hours, the reaction solution was distilled off under reduced pressure, and the residue was chloroform (100 ml).
Soxhlet extraction was performed. Thereafter, the extract was distilled off under reduced pressure, and recrystallization was repeated with THF to obtain the following formula (18).

A yellow-orange powder compound represented by: 1,4-bis [2,5-dimethoxy-4- [2- (4-pyridyl) ethenyl] phenyl] butadiene was obtained. The yield was 0.14 g, and the yield was 15.9%. The structure of the obtained compound was confirmed by ¹ HNMR for this compound.

¹ HNMR (400MHz, DMSO, ppm): δ8.58 (d, 4H, pyridyl group), 7.72 (d, 2H, ethenyl group), 7.66 (d, 4H, pyridyl group), 7.40 (d, 2H, ethenyl group) ), 7.35 (s, 2H, phenyl group), 7.34
(s, 2H, phenyl group), 7.28 (d, 2H, butadiniyl group), 7.04 (d, 2H, butadiniyl group), 3.93 (s, 6H, methoxy group), 3.90 (s, 6H, methoxy group).

Synthesis example 6
Compound (18) (40.0 mg, 0.0750 mmol) was completely dissolved in dichloromethane (50 ml), and CF ₃ SO ₃ CH ₃ (30.9 mg, 0.188 mmol) was added. After stirring at room temperature for 1 hour, the reaction solvent was distilled off under reduced pressure, and recrystallization was repeated with methanol to obtain the following formula (19).

The compound represented by: 1,4-bis (2,5-dimethoxy-4- [2- [4- (N-methyl) pyridine-1-iumyl] ethenyl] phenyl) butadiene triflate was obtained. The yield was 10.0 mg, and the yield was 15.0%. The structure of the obtained compound (19) was confirmed by ¹ HNMR, ¹³ CNMR, and elemental analysis.

¹ HNMR (400MHz, DMSO, ppm): δ8.78 (d, 4H, pyridyl group), 8.17 (d, 4H, pyridyl group), 8.04 (d, 2H, ethenyl group), 7.57 (d, 2H, ethenyl group) ), 7.43 (d, 2H, butadiniyl), 7.38 (d, 2H, phenyl), 7.41 (s, 2H, phenyl), 7.39 (s, 2H, phenyl), 7.20 (d, 2H, butadiniyl) ), 4.23 (s, 6H, methyl group), 3.95 (s, 6H, methoxy group), 3
.89 (s, 6H, methoxy group).

¹³ C NMR (100 MHz, DMSO, ppm): δ152.7, 150.7, 145.0, 134.9, 132.5, 129.3, 126.9, 123.6, 123.5, 123.3, 113.8, 110.8, 108.7, 120.7 (styrylpyridyl group), (q, CF ₃ SO ₃ ,
J = 322.1 Hz), 56.2 (methoxy group), 46.8 (methyl group bonded to nitrogen of pyridyl group).

Elemental analysis: calculated (C ₃₈ H ₃₈ F ₆ N ₂ O ₁₀ ): C, 53.02; H, 4.45; N, 3.25; F, 13.24, found: C, 52.80; H, 4.48; N, 3.37; F , 13.20%.
Example 1
Evaluation Method of Two-Photon Absorption Cross Section The evaluation of the two-photon absorption cross section of the compound of the present invention is based on Reference I (M. Sheik-Bahae, AA Said, T.-H. Wei, DJ Hagan, EW van Stryland, IEEE J. Quant. Electron. 26 (1990) 760.) was performed with reference to the open aperture type Z-scan method.

As a light source for measuring the two-photon absorption cross section, a Ti: sapphire pulse laser and an optical parametric oscillator laser excited by the laser were used. The pulse width of the pulse serving as the light source was 110 to 130 femtoseconds, the pulse repetition frequency was 1 kHz or 10 Hz, and the average power was 0.1 to 1.4 mW. The wavelength range was 570 to 1200 nm.

As described in Document I, the measurement is performed by condensing the pulse laser beam from the light source with a lens, scanning the sample to be measured in the laser beam traveling direction (Z axis), and then measuring each sample on the Z axis. The transmittance was measured at the position. From the obtained transmittance curves, incident average power, incident wavelength, incident pulse width, sample concentration, sample thickness, etc. at each sample position, Document II (K. Kamada, K. Ohta. K. Iwase, and K. Kondo, Chem. Phys. Lett., 372, 386-393 (2003)), a two-photon absorption cross section was obtained.

Measurement example of two-photon absorption cross-section (19)

The two-photon absorption cross-sectional area was measured by the above-described two-photon absorption evaluation method using a compound obtained by dissolving the compound represented by the above formula in a spectroscopic grade dimethyl sulfoxide (DMSO) as a sample. The concentration of the sample solution was 0.4 to 2.0 mM. The two-photon absorption cross sections obtained at each measurement wavelength are shown in the following table.

In the above table, the two-photon absorption cross section is expressed in GM units. 1GM is 1 × 10 ^-50 cm ⁴ · sec per molecule / photon (1GM = 1 × 10 ^-50 cm ⁴ · s / (molecule · photon)). Thus, over 1000 GM in a wide wavelength range, the maximum value was 3637 GM, and good characteristics far exceeding the conventional materials described in [Patent Document 1] were obtained.

It is a schematic diagram which shows the outline | summary of the light limiting apparatus by this invention. It is a schematic diagram which shows the outline | summary of the two-photon absorption photomolding apparatus by this invention. It is a schematic diagram which shows the outline | summary of the three-dimensional memory device using the fluorescence of a two-photon absorption material. It is a schematic diagram which shows the outline | summary of the three-dimensional memory device using the refractive index change of a two-photon absorption material. It is a schematic diagram which shows the outline | summary of the two-photon fluorescence microscope by this invention. It is a schematic diagram which shows the outline | summary of the up-conversion laser apparatus by this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Condensing apparatus 2 Light limiting material 3 Collimating apparatus 4 Pulse laser generator 5 Condensing apparatus 6 Photocurable monomer 7 Movable or fixed stage 8 Fixed or movable mirror 9 Three-dimensional optical memory material 10 Dichroic mirror 11 Photo detector 12 Two photon Absorbing material 13 Confocal optical microscope 14 Light source for detection 15 Condensing device 16 Condensing device 17 Aperture 18 Condensing device 19 Material for up-conversion laser 20 Optical resonator

Claims (16)

An ethylene compound represented by the following general formula (1);

(In the formula, R _{1 to} R ₈ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and R ₉ and R ₁₀ are the same. Or, differently, it is a group represented by the following general formula (2) or a group represented by the following general formula (3), and n represents an integer of 1 to 4.

(Wherein R ₁₁ is an alkyl group having 1 to 3 carbon atoms, A ⁻ is RSO ₃ ⁻ (wherein R is CF ₃ , phenyl, tolyl, or an alkyl group having 1 to 3 carbon atoms) ), Halogen anion, tetraphenylboron anion (Ph ₄ B ⁻ ) or ClO ₄ ⁻ , where n is 1 and R ₉ and R ₁₀ are small
When at least one is a group represented by the general formula (2), R _{1 to} R ₈ are (i) R ₁ , R ₄ , R ₅ and R ₈ are hydrogen atoms, and R ₂ , R ₃ , R ₆ and R ₇ are lower alkoxy groups;
(B) R ₁ , R ₄ , R ₆ and R ₇ are hydrogen atoms, and R ₂ , R ₃ , R ₅ and R ₈ are lower alkoxy groups;
(C) R ₂ , R ₃ , R ₅ and R ₈ are hydrogen atoms, and R ₁ , R ₄ , R ₆ and R ₇ are lower alkoxy groups;
Or (d) R ₂ , R ₃ , R ₆ and R ₇ are hydrogen atoms. ). In the general formula (1), R ₉ And R _Ten The ethylene compounds according to claim 1, which are the same or different and are groups represented by the general formula (3). In the general formula (1), R _{1 to} R ₈ are
(A) R ₁ , R ₄ , R ₅ and R ₈ are hydrogen atoms, and R ₂ , R ₃ , R ₆ and R ₇ are lower alkoxy groups;
(B) R ₁ , R ₄ , R ₆ and R ₇ are hydrogen atoms, and R ₂ , R ₃ , R ₅ and R ₈ are lower alkoxy groups;
(C) R ₂ , R ₃ , R ₅ and R ₈ are hydrogen atoms, and R ₁ , R ₄ , R ₆ and R ₇ are lower alkoxy groups;
Or (d) the ethylene-based compound according to claim 1 or 2, wherein R ₂ , R ₃ , R ₆ and R ₇ are hydrogen atoms. A two-photon absorption material comprising the compound according to claim 1. A light limiting material comprising the compound according to claim 1. A curable material for a photocurable resin for photomolding, comprising the compound according to any one of claims 1 to 3. A three-dimensional optical memory material comprising the compound according to claim 1. R ₉ and R ₁₀ are represented by the following general formula (2)

4. A fluorescent dye material for a scanning two-photon fluorescence microscope comprising the ethylene compound according to claim 1 or 3, wherein 6. A light limiting device in which the light limiting material according to claim 5 is disposed between a light collecting device and a collimating device. A two-photon absorption photomolding device equipped with a pulse laser generator, a pulse laser condensing device, a photocurable monomer container, and a mechanism for scanning a predetermined condensing position in the photocurable monomer with a laser beam. 7. A photomolding device, wherein the curable material according to claim 6 is contained in a photocurable monomer. A three-dimensional optical memory device comprising a pulse laser generator, a pulse laser condensing device, a three-dimensional optical memory material, a mechanism for scanning a predetermined condensing position of the memory material with a laser beam, and an optical readout device, In the three-dimensional memory material, R ₉ and R ₁₀ are represented by the following general formula (2):

4. A three-dimensional memory device comprising the ethylene compound according to claim 1 or 3, wherein 8. A pulse laser generator, a pulse laser condensing device, the three-dimensional optical memory material according to claim 7, a mechanism for scanning a predetermined converging position of the memory material with a laser beam, and a change in refractive index in the optical memory material are detected. A three-dimensional optical memory device equipped with a mechanism. 9. A two-photon fluorescence microscope equipped with a pulse laser generator, a pulse laser condensing device, a fluorescent dye material according to claim 8, a mechanism for scanning a predetermined condensing position of the fluorescent dye material with a laser beam, and a photodetection device . R ₉ and R ₁₀ are represented by the following general formula (2)

4. A material for an upconversion laser comprising the ethylene compound according to claim 1 or 3 which is a group represented by: 15. An upconversion laser device comprising the material according to claim 14 and an optical resonator. A two-photon absorption excitation method in which excitation by two-photon absorption is caused by irradiating the compound according to any one of claims 1 to 3 with light having a wavelength longer than the linear absorption wavelength of the compound.

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