JP2010196019A - Organic silica-based material and organic silica-based mesoporous body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic silica-based material and an organic silica-based mesoporous body which at least absorbs light with a wavelength of 600 nm or more and has meso-structure. <P>SOLUTION: The organic silica-based material contains a polymer having meso-structure of a perylene-based organic silane compound represented by formula (1), wherein at least three groups of R<SP>1</SP>to R<SP>10</SP>are substituents containing an alkoxysilyl group represented by formula (2):-(Z)<SB>m</SB>-Si(OR<SP>a</SP>)<SB>n</SB>R<SP>b</SP><SB>3-n</SB>, and a surfactant. The organic silica-based porous body comprises the polymer of the perylene-based organic silane compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic silica-based material and an organic silica-based mesoporous material, and more particularly to an organic silica-based material having a perylene bisimide skeleton and an organic silica-based mesoporous material.

  A polymer of an organic silane compound having a meso structure is an organic / inorganic hybrid material that can be expected to be applied to a light emitting material, a photocatalyst, a solar cell, and the like, and various organic silane compound polymers have been proposed.

  For example, WO 2007/034861 (Patent Document 1) discloses a crosslinked organosilane having a pyrene skeleton, anthracene skeleton, acridone skeleton, acridine skeleton, quaterphenyl skeleton, oligophenylene vinylene skeleton, or the like. Yes. As described in Patent Document 1, since a mesostructure composed of a crosslinked organosilane having a pyrene skeleton or an acridine skeleton absorbs ultraviolet rays, application to an ultraviolet-responsive photocatalyst can be expected. In addition, a mesostructure composed of a crosslinked organosilane having an anthracene skeleton, an acridone skeleton, or a quaterphenyl skeleton absorbs visible light of 400 nm or more. .

  However, the mesostructures composed of these crosslinked organosilanes have an absorption edge on the long wavelength side in the absorption spectrum of 500 nm or less, and absorb light on the longer wavelength side in order to efficiently use sunlight. A mesostructure was required.

  See also Chandra et al., Chem. Mater. 2007, Vol. 19, pp. 5347-5354 (Non-patent Document 1) discloses organic-inorganic hybrid mesoporous silica having a bis (propyliminomethyl) phenol skeleton, and Cornelius et al. Mater. Chem. 2008, Vol. 18, pp. 2587-2592 (non-patent document 2) discloses a mesoporous silica-based organic-inorganic hybrid material having a 4,4′-divinylazobenzene skeleton. These mesoporous silicas absorb light having a relatively long wavelength. However, even in these mesoporous silicas, the absorption edge on the long wavelength side of the absorption spectrum is 550 to 570 nm, and sunlight is more efficiently used. In order to use it, a mesostructure that absorbs light on the longer wavelength side was necessary.

  Meanwhile, Yang et al., Adv. Func. Mater. 2008, Vol. 18, pp. 1-10 (Non-patent Document 3), an organosilane precursor having a perylene bisimide skeleton having two alkoxysilyl groups, and an organosilica obtained by polycondensation thereof A structure is disclosed. However, even if the organosilane precursor described in Non-Patent Document 3 is used, it is difficult to obtain an organic silica structure having a mesostructure.

International Publication No. 2007/034861 Pamphlet

Chandra et al., Chem. Mater. 2007, Vol. 19, pp. 5347-5354 Cornelius et al. Mater. Chem. 2008, Vol. 18, pp. 2587-2592 Yang et al., Adv. Func. Mater. 2008, Vol. 18, pp. 1-10

  The present invention has been made in view of the above-described problems of the prior art, and includes an organic silica-based material having a mesostructure and an organic silica-based mesoporous material that can absorb at least light having a wavelength of 600 nm or more. The purpose is to provide.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have developed an organosilica material containing an organosilane compound polymer and a surfactant, and an organosilica compound comprising the organosilane compound polymer. In a porous body, by using an organic silane compound having a perylene bisimide skeleton having at least three alkoxysilyl groups as the organic silane compound, a polymer of the organic silane compound forms a mesostructure, and further an organic silica The present inventors have found that the system material and the organic silica-based porous body can absorb at least light having a wavelength of 600 nm or more, and have completed the present invention.

  That is, the organic silica material of the present invention has the following formula (1):

[In the formula (1), at least three groups of R ^{1 to} R ¹⁰ are each independently represented by the following formula (2):
_{^{- (Z) m -Si (OR}} a) n R b 3-n (2)
(In formula (2), R ^a represents an alkyl group having 1 to 8 carbon atoms, R ^b represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group having 2 to 8 carbon atoms, and Z Is selected from the group consisting of alkylene groups having 1 to 12 carbon atoms, arylene groups having 6 to 12 carbon atoms, ethenylene groups, ethynylene groups, ether groups, carbonyl groups, amino groups, amide groups, urethane groups and imide groups. 1 type of group is represented, m is an integer of 0-2, n is an integer of 1-3.)
A substituent containing an alkoxysilyl group represented by:
Groups other than the substituent containing the alkoxysilyl group among R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, One group selected from the group consisting of an aryl group having 6 to 12 carbon atoms, a phenoxy group, an acetyl group, a benzoyl group, an amino group, an amide group, a nitro group, a cyano group, and an imide group;
The groups other than the substituent containing the alkoxysilyl group among R ^{9 to} R ¹⁰ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. One kind of group selected. ]
A polymer having a mesostructure of a perylene-based organosilane compound represented by the formula: and a surfactant.

  Moreover, the organosilica mesoporous material of the present invention is characterized by comprising a polymer of a perylene-based organosilane compound represented by the formula (1).

In the organic silica-based material and the organic silica-based mesoporous material of the present invention, as the perylene-based organic silane compound, R ² , R ³ , R ⁶ and R ⁷ in the formula (1) are represented by the formula (2). What is the substituent containing the alkoxysilyl group represented is preferable.

  In the organic silica material and the organic silica mesoporous material of the present invention, it is preferable that the wavelength of the absorption edge on the long wavelength side of the absorption spectrum is 600 nm or more.

  Although the reason why the polymer of the organosilane compound forms a mesostructure by using an organosilane compound having a perylene bisimide skeleton having at least three alkoxysilyl groups as in the present invention is not necessarily clear, The inventors speculate as follows. That is, when three or more silyl groups (silica skeleton-forming sites) are introduced into a large crosslinked organic group such as a perylene bisimide skeleton, the density of silanol groups in the organosilane compound after hydrolysis increases. This is presumably because the interaction between the template surfactant micelle and the template surfactant micelle is enhanced, and the interaction between the perylene bisimide skeletons is relaxed.

  On the other hand, when only two silyl groups are introduced into the perylene bisimide skeleton, the interaction between the perylene bisimide skeletons is strong and the organic silane compound aggregates, so that it is difficult to form a regular mesostructure. Inferred. In addition, when the size of the crosslinked organic group is increased, the interaction between the silanol group in the organosilane compound after hydrolysis and the template surfactant micelle is relatively weak, so that it is difficult to form a regular mesostructure. It is assumed that

  According to the present invention, it is possible to obtain an organic silica-based material having a mesostructure and an organic silica-based mesoporous material that can absorb at least light having a wavelength of 600 nm or more.

2 is a graph showing X-ray diffraction patterns of the organic silica powder obtained in Example 1 and the porous powder obtained in Example 2. FIG. 2 is a graph showing ultraviolet / visible absorption spectra of the organic silica powder obtained in Example 1 and the porous powder obtained in Example 2. FIG. 4 is a graph showing X-ray diffraction patterns of the organic silica thin film obtained in Example 3 and the porous thin film obtained in Example 4. It is a graph which shows the ultraviolet / visible absorption spectrum of the organic silica thin film obtained in Example 3, and the porous body thin film obtained in Example 4. It is a graph which shows the X-ray-diffraction pattern of the organic silica thin film obtained in Example 5, and the porous body thin film obtained in Example 6. It is a graph which shows the ultraviolet / visible absorption spectrum of the organic silica thin film obtained in Example 5, and the porous thin film obtained in Example 6. It is a graph which shows the X-ray-diffraction pattern of the organic silica thin film obtained in Example 7, and the porous body thin film obtained in Example 8. It is a graph which shows the ultraviolet / visible absorption spectrum of the organic silica thin film obtained in Example 7, and the porous body thin film obtained in Example 8. 3 is a graph showing an X-ray diffraction pattern of organic silica obtained in Comparative Example 1.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  First, the organic silica material of the present invention will be described. The organic silica material of the present invention has the following formula (1):

A polymer having a mesostructure of a perylene-based organosilane compound (hereinafter referred to as “Si-based polymer”) and a surfactant. Thus, since the organic silica material of the present invention contains a Si-based polymer having a perylene bisimide skeleton, the wavelength of the absorption edge on the long wavelength side of the absorption spectrum is 600 nm or more, and a length of 500 nm or more. It becomes possible to efficiently absorb light of a wavelength.

In the perylene-based organosilane compound represented by the formula (1), at least three groups of R ^{1 to} R ¹⁰ in the formula (1) are each independently represented by the following formula (2):
_{^{- (Z) m -Si (OR}} a) n R b 3-n (2)
It is a substituent containing the alkoxysilyl group represented by these. It is possible to form a Si-based polymer having a meso structure by condensing a perylene-based organosilane compound having at least three substituents containing such alkoxysilyl groups.

^Ra in the formula (2) represents an alkyl group having 1 to 8 (preferably 1 to 4) carbon atoms, and among them, a methyl group or an ethyl group is preferable. R ^b represents an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms) or an allyl group having 2 to 8 carbon atoms (preferably 2 to 4 carbon atoms), and the allyl group has a substituent such as a methyl group. It may be.

  Z in the formula (2) is an alkylene group having 1 to 12 carbon atoms (preferably 1 to 6), an arylene group having 6 to 12 carbon atoms, an ethenylene group, an ethynylene group, an ether group, a carbonyl group, an amino group, Represents an amide group, a urethane group or an imide group. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, and a hexamethylene group. Examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, a pyridylene group, and a thienylene group. Among these groups, Z is preferably a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group, an ether group, or an amino group from the viewpoint of chemical stability during polymerization reaction and reduction of hydrophobicity.

  M in the formula (2) is an integer of 0 to 2, and when m is 0, Z means a single bond. When m is 2, a plurality of Z may be the same or different. For example, examples of the group composed of different Z combinations include a phenoxy group in which one is an ether group and the other is a phenyl group. In the formula (2), n is an integer of 1 to 3, and it is preferable that n is 2 or 3 from the viewpoint that the condensation reaction easily proceeds and the structure after the condensation is stable.

In the perylene-based organosilane compound represented by the formula (1), groups other than the substituent containing the alkoxysilyl group among R ^{1 to} R ⁸ in the formula (1) are each independently hydrogen. Atom, halogen atom, alkyl group having 1 to 12 carbon atoms (preferably 1 to 6), alkoxy group having 1 to 12 carbon atoms (preferably 1 to 6), aryl group having 6 to 12 carbon atoms, phenoxy group, acetyl Group, benzoyl group, amino group, amide group, nitro group, cyano group or imide group. Among these, a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group, and a phenoxy group are preferable from the viewpoint of chemical stability and high density of perylene groups in the polymer.

In the perylene-based organosilane compound represented by the formula (1), groups other than the substituent containing the alkoxysilyl group among R ^{9 to} R ¹⁰ in the formula (1) are each independently hydrogen. An atom, an alkyl group having 1 to 12 (preferably 1 to 6) carbon atoms, or an aryl group having 6 to 12 carbon atoms. Among these, 1-ethylpropyl group, butyl group, 2-ethylhexyl group, and cyclohexyl group are preferable from the viewpoint of achieving both improvement of the solubility of the compound and high density of perylene groups in the polymer.

In the present invention, such perylene-based organosilane compounds may be used alone or in combination of two or more. From the viewpoint that three or more alkoxysilyl groups can be easily introduced among such perylene-based organosilane compounds, R ² , R ³ , R ⁶ and R ⁷ in the formula (1) are represented by the formula An organosilane compound which is a substituent containing an alkoxysilyl group represented by (2), and R ¹ , R ⁴ , R ⁵ and R ⁸ in the formula (1) are alkoxy represented by the formula (2) The organosilane compound which is a substituent containing a silyl group is preferred, and the former organosilane compound is more preferred.

The Si-based polymer used in the present invention is a polymer of such a perylene-based organic silane compound and has a meso structure. The structural formula of such a Si-based polymer depends on the type of perylene-based organosilane compound to be polymerized. For example, an organic silane compound in which R ² , R ³ , R ⁶ and R ⁷ in the formula (1) are substituents containing an alkoxysilyl group represented by the formula (2), that is, the following formula (3 ):

When the perylene-based organosilane compound represented by formula (1) is polymerized, the Si-based polymer has the following formula (4):

It has what has a repeating unit represented by these.

R ¹ , R ⁴ , R ⁵ and R ^{8 to} R ¹⁰ in the formulas (3) and (4) are groups other than the substituent containing the alkoxysilyl group in the formula (1), respectively. ¹ has the same meaning as ^R 4, ^{R 5} and ^R 8 ^{to R 10.} Formula (3) and (4) in Z, m and ^{R b} are each Z in the formula (2), the same meaning as m and ^{R b. R a} and n in the formula (3) are respectively the same as ^{R a} and n in the formula (2). In the formula (4), i is an integer of 1 to 3, j is an integer of 0 to 2, and 1 ≦ i + j ≦ 3. The combination of i and j need not be the same for all silyl groups in the Si-based polymer. Further, when R ^b is an allyl group, the allyl group is eliminated by hydrolysis, and therefore the value of (3-n) in the formula (3) and the value of the formula (3-i-j) are not necessarily the same. do not do.

From the viewpoint that it is easy to introduce a substituent containing an alkoxysilyl group represented by the formula (2) among the perylene-based organosilane compounds represented by the formula (3), R in the formula (3) ¹ , R ⁴ , R ⁵ and R ⁸ are preferably hydrogen atoms, and n in the formula (3) is 2 or 3 from the viewpoint of increasing the degree of crosslinking of the polymer and stabilizing the structure. Those are more preferred.

  In the present invention, a copolymer of a perylene-based organic silane compound represented by the formula (1) and another organic silane compound can also be used as the Si-based polymer. Examples of the other organic silane compounds include dialkoxysilanes such as dimethoxysilane and diethoxysilane; trialkoxysilanes such as trimethoxysilane and triethoxysilane; tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane; Triethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethylene, 1,2-bis (triethoxysilyl) acetylene, 1,4-bis (triethoxysilyl) benzene, 4,4′-bis (tri Well-known alkoxysilane compounds, such as organic group bridge | crosslinking type alkoxysilanes, such as an ethoxy silyl) biphenyl, are mentioned. These alkoxysilane compounds may be used alone or in combination of two or more.

  In the case of (co) polymerizing the perylene-based organic silane compound and, if necessary, the other organic silane compounds (hereinafter collectively referred to as “silane monomers”), the ratio of the perylene-based organic silane compound is: 10-100 mass% is preferable with respect to 100 mass% of all the silane monomers used for (co) polymerization, and 50-100 mass% is more preferable. The conditions for the (co) polymerization reaction are not particularly limited, but water or a mixed solvent of water and an organic solvent is used as a solvent, and the silane monomer is hydrolyzed and condensed in the presence of an acid or base catalyst. It is preferable. Suitable organic solvents used at this time include alcohol, tetrahydrofuran, acetone and the like, and the content of the organic solvent when used as a mixed solvent is preferably about 5 to 99% by weight. Examples of the acid catalyst include mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, and the solution in the case of using the acid catalyst is preferably acidic with a pH of 6 or less (more preferably 2 to 5). . Furthermore, examples of the base catalyst include sodium hydroxide, ammonium hydroxide, potassium hydroxide, and the like. When the base catalyst is used, the solution has a basic pH of 8 or more (more preferably 9 to 11). Preferably there is.

  The concentration of the silane monomer in such a (co) polymerization step is preferably about 0.0055 to 0.33 mol / L in terms of silicon concentration. The conditions (temperature, time, etc.) in the (co) polymerization step are not particularly limited and are appropriately selected according to the silane monomer to be used, the target Si-based polymer, and the like. The silane monomer is preferably hydrolyzed and condensed at a temperature of about 100 ° C. for a time of about 1 to 48 hours.

  When the perylene-based organosilane compound is (co) polymerized, the silyl group in the formula (1) is usually hydrolyzed to form a silanol group (Si—OH), and a siloxane bond (Si -O-Si) is formed. At this time, even if a part of the silanol group is not converted into a siloxane bond and remains as it is or an allyl group bonded to Si remains as it is, the light absorption of the organic silica material is not affected.

  The organic silica material of the present invention may contain a surfactant in addition to the Si polymer. This surfactant has an effect that the form of the polymer can be easily controlled by complexing with the Si-based polymer.

  Such a surfactant is usually left as it is without removing the one used when preparing the Si polymer. Further, by carrying out the (co) polymerization in the presence of a surfactant, the Si polymer has a structure (mesostructure) having mesopores having a central pore diameter of 1 to 30 nm in a pore diameter distribution curve. ) Having a mesoporous material.

  The central pore diameter is a curve (pore diameter distribution curve) in which a value (dV / dD) obtained by differentiating the pore volume (V) with respect to the pore diameter (D) is plotted against the pore diameter (D). ) At the maximum peak, and can be determined by the method described below. That is, the mesoporous material is cooled to a liquid nitrogen temperature (−196 ° C.), nitrogen gas is introduced, the adsorption amount is determined by a constant volume method or a gravimetric method, and then the pressure of the introduced nitrogen gas is gradually increased. Then, the adsorption amount of nitrogen gas with respect to each equilibrium pressure is plotted to obtain an adsorption isotherm. Using this adsorption isotherm, a pore size distribution curve can be obtained by a calculation method such as Cranston-Inklay method, Pollimore-Heal method, or BJH method.

Such a mesoporous material preferably contains 60% or more of the total pore volume in a range of ± 40% of the center pore diameter in the pore diameter distribution curve. A mesoporous material satisfying this condition means that the pore diameter is very uniform. The specific surface area of the mesoporous material is not particularly limited, but is preferably 700 m ² / g or more. The specific surface area can be calculated as a BET specific surface area from the adsorption isotherm using the BET isotherm adsorption equation.

  Further, such a mesoporous material preferably has one or more peaks at a diffraction angle corresponding to a d value of 1.5 to 30.5 nm in its X-ray diffraction (XRD) pattern. The X-ray diffraction peak means that a periodic structure having a d value corresponding to the peak angle is present in the sample. Therefore, having one or more peaks at a diffraction angle corresponding to a d value of 1.5 to 30.5 nm indicates that the pores are regularly arranged at intervals of 1.5 to 30.5 nm. means.

  The surfactant used in preparing the mesostructured Si-based polymer according to the present invention is not particularly limited, and may be any of cationic, anionic, and nonionic, specifically, Chloride, bromide, iodide or hydroxide such as alkyltrimethylammonium, alkyltriethylammonium, dialkyldimethylammonium, benzylammonium; fatty acid salt, alkylsulfonate, alkylphosphate, polyethylene oxide nonionic surfactant, Primary alkylamines are listed. These surfactants may be used alone or in combination of two or more.

Among the surfactants, examples of the polyethylene oxide nonionic surfactant include a polyethylene oxide nonionic surfactant having a hydrocarbon group as a hydrophobic component and polyethylene oxide as a hydrophilic portion. Such surfactants, for example, the general formula _{C n H 2n + 1 (OCH} 2 CH 2) expressed in m OH, n is 10 to 30, m can be preferably used those which are 1 to 30. Further, esters of fatty acids such as oleic acid, lauric acid, stearic acid, and palmitic acid and sorbitan, or compounds obtained by adding polyethylene oxide to these esters can also be used as the polyethylene oxide nonionic surfactant.

Furthermore, a triblock copolymer type polyalkylene oxide can also be used as the polyethylene oxide nonionic surfactant. Examples of such surfactants include those composed of polyethylene oxide (EO) and polypropylene oxide (PO) and represented by the general formula (EO) _x (PO) _y (EO) _x . x and y represent the number of repetitions of EO and PO, respectively, x is preferably 5 to 110, y is preferably 15 to 70, x is preferably 13 to 106, and y is more preferably 29 to 70. Examples of the triblock copolymer include (EO) ₁₉ (PO) ₂₉ (EO) ₁₉ , (EO) ₁₃ (PO) ₇₀ (EO) ₁₃ , (EO) ₅ (PO) ₇₀ (EO) ₅ , (EO) _13. (PO) ₃₀ (EO) ₁₃ , (EO) ₂₀ (PO) ₃₀ (EO) ₂₀ , (EO) ₂₆ (PO) ₃₉ (EO) ₂₆ , (EO) ₁₇ (PO) ₅₆ (EO) ₁₇ , (EO ) ₁₇ (PO) ₅₈ (EO) ₁₇ , (EO) ₂₀ (PO) ₇₀ (EO) ₂₀ , (EO) ₈₀ (PO) ₃₀ (EO) ₈₀ , (EO) ₁₀₆ (PO) ₇₀ (EO) ₁₀₆ , (EO) ₁₀₀ (PO) ₃₉ (EO) ₁₀₀ , (EO) ₁₉ (PO) ₃₃ (EO) ₁₉ , (EO) ₂₆ (PO) ₃₆ (EO) ₂₆ may be mentioned. These triblock copolymers are available from BASF, Aldrich, etc., and triblock copolymers having desired x and y values can be obtained at a small scale production level.

Further, a star diblock copolymer in which two polyethylene oxide (EO) chains-polypropylene oxide (PO) chains are bonded to two nitrogen atoms of ethylenediamine can also be used as the polyethylene oxide nonionic surfactant. Examples of such star diblock copolymers include those represented by the general formula ((EO) _x (PO) _y ) ₂ NCH ₂ CH ₂ N ((PO) _y (EO) _x ) ₂ . Here, x and y represent the number of repetitions of EO and PO, respectively, x is preferably 5 to 110, y is preferably 15 to 70, x is 13 to 106, and y is 29 to 70. preferable.

In the organic silica-based material of the present invention, among the surface-active agent, since it is possible ordering of the pores to obtain a high mesoporous, alkyltrimethylammonium _{[C p H 2p + 1 N} (CH 3) 3] of It is preferable to use a salt (preferably a halide salt). In that case, the alkyl group in the alkyltrimethylammonium preferably has 8 to 22 carbon atoms. Such surfactants include octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, decyl trimethyl ammonium bromide, octyl trimethyl ammonium bromide, docosyl trimethyl ammonium chloride, etc. Is mentioned.

  In the case of producing the Si-based polymer according to the present invention using the surfactant, the perylene-based organosilane compound represented by the formula (1) is hydrolyzed and dissolved in a solvent containing the surfactant. By condensing, a porous precursor (organic silica-based material) in which the surfactant is introduced into the Si-based polymer is obtained. The concentration of the surfactant in the solution is preferably 1 to 20% by mass. When the concentration of the surfactant is less than the lower limit, pore formation tends to be incomplete. On the other hand, when the concentration exceeds the upper limit, the amount of the unreacted surfactant remaining in the solution increases and becomes finer. There is a tendency that the uniformity of the holes tends to decrease.

  In the organic silica material of the present invention, the content of the Si polymer is preferably 10 to 80% by mass, and more preferably 30 to 70% by mass with respect to 100% by mass of the organic silica material. When the content of the Si-based polymer is less than the lower limit, the amount of light absorbed by the Si-based polymer tends to decrease. On the other hand, when the upper limit is exceeded, the order of the mesostructure tends to decrease. Moreover, as content rate of the said surfactant, 20-90 mass% is preferable with respect to 100 mass% of said organic silica type materials, and 30-70 mass% is more preferable. When the content of the surfactant is less than the lower limit, the order of the mesostructure tends to be lowered, and the association of the organic groups in the Si-based polymer tends not to be sufficiently suppressed. There is a tendency that the amount of light absorbed by the polymer is likely to decrease.

  The form of the organic silica material of the present invention is not particularly limited, and examples thereof include a particulate shape, a thin film shape, and a pattern shape obtained by patterning the thin film into a predetermined shape. The organic silica material of the present invention may be supported on mesoporous silica such as FSM.

  When producing the organic silica material of the present invention, the silane monomer may be polymerized after mixing the silane monomer and the surfactant. As a result, the surfactant can be filled in the pores of the polymer of the silane monomer (Si polymer according to the present invention), and the quantum yield of the organic silica material can be kept high. .

  In the case of producing a thin-film organic silica-based material, first, the silane monomer is added to an acidic solution containing the surfactant (for example, an aqueous solution or alcohol solution of hydrochloric acid, nitric acid, etc.). A sol solution containing the partial polymer is produced by stirring and reacting (partial hydrolysis and partial condensation reaction). Since such hydrolysis reaction of the silane monomer is likely to occur in a low pH region, partial polymerization can be promoted by lowering the pH of the system. At this time, the pH is preferably 6 or less, and more preferably 4 or less. Further, the reaction temperature at that time is preferably about 15 to 25 ° C., and the reaction time is preferably about 30 minutes to 1 day.

  Next, a thin-film organic silica-based material can be produced by applying the sol solution thus obtained to a substrate. There is no restriction | limiting in particular as a method of apply | coating the said sol solution to a board | substrate, Various coating methods can be employ | adopted suitably. Examples of the method include a solution casting method, a coating method using a bar coater, a roll coater, a gravure coater, and the like, a method such as dip coating, spin coating, and spray coating. Furthermore, it is also possible to form a patterned organic silica material on a substrate by applying a sol solution by an ink jet method.

  Next, it is preferable to dry the obtained thin film at about 25-120 degreeC, and to advance the polycondensation reaction of the said partial polymer, and to form a three-dimensional crosslinked structure. The average film thickness of the obtained thin film is preferably 2 μm or less, and more preferably 0.1 to 0.5 μm.

  Such a thin-film organic silica-based material can also be obtained in accordance with a method described in JP-A No. 2001-130911.

  Next, the organosilica mesoporous material of the present invention will be described. The organosilica mesoporous material of the present invention has the following formula (1):

A polymer having a mesostructure of a perylene-based organosilane compound (Si-based polymer). ^R 1 ^{to R 10} in the formula (1) in the organic mesoporous silica material of the present invention has the same meaning as ^R 1 ^{to R 10} in the formula (1) in the organic silica-based material. Since the organosilica mesoporous material of the present invention contains a Si polymer having a perylene bisimide skeleton, the wavelength of the absorption edge on the long wavelength side of the absorption spectrum is 600 nm or more, and the long wavelength of 500 nm or more. Light can be efficiently absorbed. Even if a part of silanol group remains in the Si polymer or an allyl group bonded to Si does not affect the light absorption of the organosilica mesoporous material.

  The structural formula of the Si-based polymer in the organic silica-based mesoporous material of the present invention depends on the type of perylene-based organic silane compound to be polymerized. For example, the perylene-based organosilane compound is represented by the following formula (3)

The Si-based polymer is represented by the following formula (4):

It has what has a repeating unit represented by these.

In the organosilica mesoporous material of the present invention, R ¹ , R ⁴ , R ⁵ , R ^{8 to} R ¹⁰ , Z, m and R ^b in the formulas (3) and (4) are the same as those in the organosilica material. equation (3) and (4) ^R 1 ^{in, R 4, R 5, R} 8 ~R 10, Z, is synonymous with m and ^{R b.} R ^a and n in the formula (3) in the said organic mesoporous silica material has the same meaning as R ^a and n in the formula (3) in the said organic silica materials. I and j in the formula (4) in the organosilica-based mesoporous material have the same meanings as i and j in the organosilica-based material, and the combination of i and j is all silyl in the Si-based polymer. The groups need not be the same. Further, when R ^b is an allyl group, the allyl group is eliminated by hydrolysis, and therefore the value of (3-n) in the formula (3) and the value of the formula (3-i-j) are not necessarily the same. do not do.

  Such an organic silica-based mesoporous material can be produced by removing the surfactant from the organic silica-based material of the present invention. As a method for removing the surfactant, for example, (i) a mesostructured Si-based polymer and a surfactant are contained in an organic solvent (for example, ethanol) having high solubility in the surfactant. A method of removing the surfactant by immersing the organic silica material, (ii) firing the organic silica material of the present invention containing a mesostructured Si polymer and a surfactant at 250 to 550 ° C. And (iii) immersing the organic silica-based material of the present invention containing a mesostructured Si-based polymer and a surfactant in an acidic solution (for example, a hydrochloric acid acidic alcohol solution). An ion exchange method in which the surfactant is heated and exchanged with hydrogen ions; (iv) an organic silica-based material of the present invention containing a mesostructured Si-based polymer and a surfactant is heated with an acidic vapor (for example, , Exposed to hydrochloric acid vapor) And (v) a method of eluting the surfactant into the organic solvent by immersing it in an organic solvent (for example, ethanol), and (v) the organic silica of the present invention containing a mesostructured Si-based polymer and a surfactant. Examples include a method in which a system material is exposed to heated basic vapor (for example, ammonia water vapor) and then immersed in an organic solvent (for example, ethanol) to elute the surfactant into the organic solvent. Can do. The treatment conditions in these methods can be appropriately set depending on the type of surfactant, organic solvent, acidic vapor, basic vapor to be used.

  The form of the organic silica-based porous material of the present invention is not particularly limited, and examples thereof include a particulate shape, a thin film shape, and a pattern shape obtained by patterning the thin film into a predetermined shape. Depends on the form of Further, the organic silica based porous material of the present invention may be supported on mesoporous silica such as FSM.

  When the organosilica mesoporous material of the present invention is produced as a powder, it may be used as it is, or may be molded and used as necessary. The means for molding is not particularly limited, but extrusion molding, tableting molding, rolling granulation, compression molding, CIP and the like are preferable. The shape can be determined according to the place of use, method, and the like, and examples thereof include a columnar shape, a crushed shape, a spherical shape, a honeycomb shape, an uneven shape, and a corrugated plate shape.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, the ultraviolet / visible absorption spectrum of the obtained mesoporous material of the organic silica powder and the organic silica thin film was measured using “FP-6500 Spectrofluorometer” manufactured by JASCO.

(Synthesis Example 1)
<Synthesis of N, N′-bis (1-ethylpropyl) -2,5,8,11-tetrakis [2- (trimethoxysilyl) ethyl] perylene-3,4: 9,10-tetracarboxylic acid bisimide>
First, a perylene-3,4: 9,10-tetracarboxylic dianhydride (1.12 g, 3.0 mmol), imidazole (6.0 g) and 1-ethylpropylamine (1 .75 mL, 15 mmol). This mixed solution is heated at 160 ° C. for 4 hours, and the following reaction formula (I):

The reaction represented by The obtained reaction solution was cooled to room temperature, 1 mol / L aqueous HCl solution was added, and unreacted amine and imidazole were separated by filtration. The obtained reaction product was separated by silica gel column chromatography using dichloromethane as a developing solvent. Thereafter, recrystallization was performed using dichloromethane and methanol to obtain a red powder (1.48 g, yield 93%).

This red powder was identified by ¹ H-NMR measurement and confirmed to be N, N′-bis (1-ethylpropyl) -perylene-3,4: 9,10-tetracarboxylic acid bisimide. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.92 (t, J = 7.4 Hz, 12H), 1.90-1.98 (m, 4H), 2.22-2.33 (m, 4H) ), 5.04-5.11 (m, 2H), 8.63 (d, J = 8.1 Hz, 4H), 8.68 (d, J = 8.1 Hz, 4H).

Next, the N, N′-bis (1-ethylpropyl) -perylene-3,4: 9,10-tetracarboxylic acid bisimide (53.0 mg, 0.10 mmol) and RuH ₂ (CO) were placed in a Schlenk flask. (PPh ₃ ) ₃ (5.5 mg, 0.006 mmol) was added, and nitrogen substitution was performed. Vinyltrimethoxysilane (0.15 mL, 1.0 mmol) and mesitylene (0.30 mL) were added thereto, and the mixture was stirred for 36 hours while heating at 165 ° C., and the following reaction formula (II):

The reaction represented by The obtained reaction solution was added to tetrahydrofuran as it was and dissolved, and the reaction product was quantitatively isolated by GPC polystyrene gel (biobeads). The obtained reaction product contained a small amount of mesitylene, and mesitylene was removed under high vacuum to obtain a dark red solid (112 mg, yield 100%).

This dark red solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, ultraviolet / visible absorption spectrum measurement, fluorescence spectrum measurement and HR-MS measurement, and N, N′-bis (1-ethylpropyl) -2 , 5,8,11-tetrakis [2- (trimethoxysilyl) ethyl] perylene-3,4: 9,10-tetracarboxylic acid bisimide. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.91 (t, J = 7.2 Hz, 12H), 1.20-1.25 (m, 8H), 1.87-1.95 (m, 4H) ), 2.20-2.28 (m, 4H), 3.57-3.63 (m, 8H), 3.68 (s, 36H), 5.06-5.11 (m, 2H), 8.43 (s, 4H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 11.04, 11.55, 25.26, 30.53, 50.29, 57.29, 120.14, 124.46, 126.82, 132.08 133.19, 152.19, 164.34.
UV / visible absorption spectrum _{(toluene): λ max [nm] (} ε [M -1 cm -1]) = 386 (8900), 456.5 (15000), 486.5 (38000), 522.5 (56000 ).
Fluorescence spectra _{(toluene, λ ex = 523nm): λ} em [nm] = 534,576.
HR-MS (ESI-MS) : m / z = 1157.4188, calcd for (C 54 H 78 N 2 O 16 Si 4 Cl) - = 1157.4122 ([M + Cl] -).

(Synthesis Example 2)
<Synthesis of N, N'-dibutyl-1,6,7,12-tetrakis [4- (triethoxysilyl) phenoxy] perylene-3,4: 9,10-tetratetracarboxylic acid bisimide>
First, propionic acid (30 mL) was added to 1,6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboxylic dianhydride (1.94 g, 3.66 mmol) and butylamine (1.81 mL). , 1.34 g, 18.3 mmol), and heated under reflux for 12 hours, the following reaction formula (III):

The reaction represented by The resulting reaction solution was cooled to room temperature, ethanol (100 mL) was added, and the resulting red precipitate was collected by suction filtration. The residue was washed with saturated aqueous sodium hydrogen carbonate solution, water and ethanol, and then dried in vacuo to give a red solid (2.08 g, yield 89%).

This red solid was identified by ¹ H-NMR measurement and confirmed to be N, N′-dibutyl-1,6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboxylic acid bisimide. . The results are shown below.
^{1 H-NMR (400MHz, CDCl} 3): δ8.67 (s, 4H), 4.22 (t, J = 7.4Hz, 4H), 1.74 (m, 4H), 1.47 (m, 4H), 1.01 (t, J = 7.4 Hz, 6H).

  Next, the N, N′-dibutyl-1,6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboxylic acid bisimide (1.0 g, 1.56 mmol), 4-iodophenol ( 2.64 g, 12.0 mmol), potassium carbonate (0.72 g, 5.24 mmol) and N-methylpyrrolidone (NMP, 16 mL) were mixed, stirred for 3 hours while heating at 140 ° C., and the following reaction formula (IV ):

The reaction represented by The resulting reaction solution was cooled to room temperature, poured into water (100 mL), and stirred for 1 hour. The resulting precipitate was collected by suction filtration and then redissolved in chloroform (50 mL). Thereafter, methanol (200 mL) was added for reprecipitation, the precipitate was collected by suction filtration, and the residue was dried under vacuum to obtain a purple solid (1.60 g).

This purple solid was identified by ¹ H-NMR measurement, and N, N′-dibutyl-1,6,7,12-tetrakis (4-iodophenoxy) perylene-3,4: 9,10-tetracarboxylic acid bisimide I confirmed that there was. The results are shown below. This purple solid contained a part of iodine (about 10%) replaced with a hydrogen atom.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.15 (s, 4H), 7.58 (d, J = 8.8 Hz, 8H), 6.66 (d, J = 8.8 Hz, 8H), 4.11 (t, J = 7.6 Hz, 4H), 1.65 (m, 4H), 1.40 (m, 4H), 0.95 (t, J = 7.3 Hz, 6H).

Next, in an argon atmosphere, the N, N′-dibutyl-1,6,7,12-tetrakis (4-iodophenoxy) perylene-3,4: 9,10-tetracarboxylic acid bisimide (1.0 g, _{0.728mmol), Rh [(cod)} (CH 3 CN) 2] BF 4 (27.7mg, 0.073mmol) and tetrabutylammonium iodide (1.08 g, 2.91 mmol) were mixed and to this mixture Dehydrated dimethylformamide (DMF, 25 mL) and dehydrated triethylamine (TEA, 1.22 mL) were added and cooled to 0 ° C. Thereafter, triethoxysilane (1.07 mL, 0.957 g, 5.82 mmol) was added and stirred at 80 ° C. for 3 hours, followed by the following reaction formula (V):

The reaction represented by After cooling the obtained reaction solution to room temperature, the solvent was distilled off under reduced pressure, diethyl ether (50 mL) was added to the residue, and the mixture was vigorously stirred. This solution was suction filtered using Celite and activated carbon, and the filtrate was concentrated and dried under reduced pressure to obtain a purple solid (0.5 g).

This purple solid was identified by ¹ H-NMR measurement, and N, N′-dibutyl-1,6,7,12-tetrakis [4- (triethoxysilyl) phenoxy] perylene-3,4: 9,10-tetra It was confirmed that it was a tetracarboxylic acid bisimide. The results are shown below. This purple solid contained a triethoxysilyl group partly substituted (approximately 15%) by hydrogen atoms.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.22 (s, 4H), 7.56 (d, J = 8.7 Hz, 8H), 6.90 (d, J = 8.7 Hz, 8H), 4.12 (t (br), 4H), 3.87 (q, J = 6.8 Hz, 24H), 1.66 (m, 4H), 1.41 (m, 4H), 1.27 (t , J = 6.8 Hz, 36H), 0.94 (t, J = 7.4 Hz, 6H).

(Synthesis Example 3)
<Synthesis of N, N'-bis [4- (triethoxysilyl) phenyl] -perylene-3,4: 9,10-tetracarboxylic acid bisimide>
First, under an argon atmosphere, perylene-3,4: 9,10-tetracarboxylic dianhydride (2.35 g, 6.0 mmol), zinc acetate (0.85 g) and quinoline (45 mL) were mixed, and 100 The mixture was stirred for 30 minutes while heating at ° C. To this mixture, 4-iodoaniline (6.57 g, 30.0 mmol) was added and stirred for 24 hours while heating at 200 ° C. The following reaction formula (VI):

The reaction represented by The resulting reaction solution was cooled to room temperature, poured into ethanol (350 mL), and the resulting precipitate was collected by suction filtration. The residue was dispersed in a 5% by mass aqueous potassium carbonate solution (500 mL), heated and stirred at 70 ° C., and then collected by suction filtration. After this operation was repeated twice, the residue was dispersed in methanol (100 mL), heated and stirred at 70 ° C., and then collected by suction filtration. Thereafter, the residue was vacuum-dried to obtain a dark red solid (4.56 g, yield 96%). Since this dark red solid was insoluble, no NMR measurement was performed, but it was N, N′-bis (4-iodophenyl) -perylene-3,4: 9,10-tetracarboxylic acid bisimide. it is conceivable that.

Next, in an argon atmosphere, the N, N′-bis (4-iodophenyl) -perylene-3,4: 9,10-tetracarboxylic acid bisimide (0.79 g, 1.0 mmol) and Rh [(cod ) (CH ₃ CN) ₂ ] BF ₄ (19.0 mg, 0.050 mmol), and to this mixture was added dehydrated dimethylformamide (DMF, 20 mL) and dehydrated triethylamine (TEA, 0.84 mL) at 0 ° C. Cooled to. Thereafter, triethoxysilane (0.74 mL, 0.657 g, 4.0 mmol) was added and stirred at 80 ° C. for 4 hours, followed by the following reaction formula (VII):

The reaction represented by After the obtained reaction solution was cooled to room temperature, the solvent was distilled off under reduced pressure, and chloroform (50 mL) was added to the residue. The solution was suction filtered using Celite and activated carbon, and the resulting chloroform solution was quickly washed with water using a separatory funnel. The separated organic layer was dried over anhydrous magnesium sulfate and then filtered, and the filtrate was concentrated under reduced pressure. Hexane (100 mL) was added to this concentrated solution and stirred for 30 minutes, and then centrifuged (3500 rpm, 5 minutes) to recover the solid component, followed by vacuum drying to obtain a dark red solid (0.33 g, 38% yield). )

This dark red solid was identified by ¹ H-NMR measurement and confirmed to be N, N′-bis [4- (triethoxysilyl) phenyl] -perylene-3,4: 9,10-tetracarboxylic acid bisimide. . The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.73 (d, J = 8.5 Hz, 4H), 8.63 (d, J = 8.5 Hz, 4H), 7.89 (d, J = 8 .4 Hz, 4H), 7.39 (d, J = 8.4 Hz, 4H), 3.95 (q, J = 7.0 Hz, 12H), 1.30 (t, J = 7.0 Hz, 18H) .

Example 1
<Preparation of organosilica powder comprising perylene bisimide skeleton-containing Si-based polymer / surfactant>
Cationic surfactant (trimethyloctadecyl ammonium chloride, 50 mg), water (3 mL) and 6 mol / L aqueous sodium hydroxide solution (0.05 mL) were mixed and stirred at room temperature. To this mixture, N, N′-bis (1-ethylpropyl) -2,5,8,11-tetrakis [2- (trimethoxysilyl) ethyl] perylene-3, 4: 9, obtained in Synthesis Example 1 was added. A solution of 10-tetracarboxylic acid bisimide (50 mg) dissolved in tetrahydrofuran (0.3 mL) was added, and the mixture was stirred at room temperature for 24 hours, and further heated at 95 ° C. for 24 hours. The generated precipitate was collected by suction filtration, washed with water, and then vacuum dried to obtain a reddish brown organic silica powder (60 mg) composed of a perylene bisimide skeleton-containing Si polymer / trimethyloctadecyl ammonium chloride.

  The X-ray diffraction pattern of the obtained powder is shown in FIG. 1, and the ultraviolet / visible absorption spectrum is shown in FIG. This organosilica powder was confirmed to have a mesostructure with a period of 4.1 nm. It was also confirmed that it has an absorption maximum near a wavelength of 530 nm, and the absorption edge on the long wavelength side of the absorption spectrum is 600 nm or more.

(Example 2)
<Preparation of perylene bisimide skeleton-containing Si-based porous powder>
The organic silica powder prepared in the same manner as in Example 1 was dispersed in a mixed solution of ethanol (10 mL) and concentrated hydrochloric acid (0.1 mL). After this dispersion was heated at 60 ° C. for 12 hours, the precipitate was collected by suction filtration and washed with ethanol to remove trimethyloctadecyl ammonium chloride from the organic silica powder. The obtained powder was vacuum-dried to obtain a perylene bisimide skeleton-containing Si-based porous powder (30 mg).

  The X-ray diffraction pattern of the obtained porous powder is shown in FIG. 1, and the ultraviolet / visible absorption spectrum is shown in FIG. This porous powder was confirmed to have a mesoporous structure with a period of 3.4 nm. It was also confirmed that it has an absorption maximum near a wavelength of 530 nm, and the absorption edge on the long wavelength side of the absorption spectrum is 600 nm or more.

(Example 3)
<Preparation of organic silica thin film comprising perylene bisimide skeleton-containing Si polymer / surfactant>
Mixed solvent of tetrahydrofuran and ethanol (mass ratio 1: 1, 0.5 mL), nonionic surfactant Brij76 (trade name, manufactured by Aldrich, chemical formula: C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH, 12 mg) N, N′-bis (1-ethylpropyl) -2,5,8,11-tetrakis [2- (trimethoxysilyl) ethyl] perylene-3,4: 9,10-tetra obtained in Synthesis Example 1 Carboxylic acid bisimide (15 mg), water (10 μL) and 2 mol / L hydrochloric acid (2 μL) were mixed to prepare a uniform solution, which was stirred at room temperature for 24 hours to prepare a sol solution.

  The obtained sol solution was spin-cast on a quartz substrate to obtain a red organic silica thin film composed of a perylene bisimide skeleton-containing Si polymer / surfactant.

  The X-ray diffraction pattern of the obtained thin film is shown in FIG. 3, and the ultraviolet / visible absorption spectrum is shown in FIG. This organic silica thin film was confirmed to have a mesostructure with a period of 5.7 nm. Moreover, it has absorption maximum in wavelength 490nm and 530nm vicinity, and it was also confirmed that the absorption edge of the long wavelength side of an absorption spectrum is 600 nm or more.

Example 4
<Preparation of perylene bisimide skeleton-containing Si-based porous thin film>
The organic silica thin film prepared in the same manner as in Example 3 was exposed to vapor of 28% by weight ammonia water at 60 ° C. for 6 hours, and then immersed in ethanol at 60 ° C. for 6 hours to remove the surfactant Brij76 from the organic silica thin film. Removed. The obtained thin film was dried under reduced pressure to obtain a perylene bisimide skeleton-containing Si-based porous thin film.

  The X-ray diffraction pattern of the obtained porous thin film is shown in FIG. 3, and the ultraviolet / visible absorption spectrum is shown in FIG. This porous thin film was confirmed to have a mesoporous structure with a period of 5.7 nm. It was also confirmed that it has an absorption maximum near a wavelength of 550 nm, and the absorption edge on the long wavelength side of the absorption spectrum is 600 nm or more.

(Example 5)
<Preparation of organic silica thin film comprising perylene bisimide skeleton-containing Si polymer / surfactant>
Nonionic surfactant P123 (trade name, manufactured by Aldrich, chemical formula: H (OCH ₂ CH ₂ ) ₂₀ (OCH ₂ CH (CH ₃ )) ₇₀ (OCH ₂ CH) instead of nonionic surfactant Brij76 ₂₎ 20 _OH, 12 mg) except for using, to obtain an organic silica film of the red consisting a manner perylenebisimides skeleton Si polymer / surfactant as in example 3.

  The X-ray diffraction pattern of the obtained thin film is shown in FIG. 5, and the ultraviolet / visible absorption spectrum is shown in FIG. This organic silica thin film was confirmed to have a mesostructure with a period of about 8.5 nm. Moreover, it has absorption maximum in wavelength 490nm and 530nm vicinity, and it was also confirmed that the absorption edge of the long wavelength side of an absorption spectrum is 600 nm or more.

(Example 6)
<Preparation of perylene bisimide skeleton-containing Si-based porous thin film>
A perylene bisimide skeleton-containing Si-based porous material in the same manner as in Example 4 except that an organic silica thin film prepared in the same manner as in Example 5 was used instead of the organic silica thin film prepared in the same manner as in Example 3. A thin film was obtained.

  The X-ray diffraction pattern of the obtained porous thin film is shown in FIG. 5, and the ultraviolet / visible absorption spectrum is shown in FIG. This porous thin film was confirmed to have a mesoporous structure with a period of about 8.0 nm. It was also confirmed that it has an absorption maximum near the wavelength of 540 nm, and the absorption edge on the long wavelength side of the absorption spectrum is 600 nm or more.

(Example 7)
<Preparation of organic silica thin film comprising perylene bisimide skeleton-containing Si polymer / surfactant>
The amount of mixed solvent of tetrahydrofuran and ethanol (mass ratio 1: 1) was changed to 0.7 mL, the amount of nonionic surfactant Brij76 was changed to 16 mg, and N, N′-bis (1-ethylpropyl) -2,5,8,11-tetrakis [2- (trimethoxysilyl) ethyl] perylene-3,4: 9,10-tetracarboxylic acid bisimide obtained in Synthesis Example 2 N, N'-dibutyl- Except that 1,6,7,12-tetrakis [4- (triethoxysilyl) phenoxy] perylene-3,4: 9,10-tetratetracarboxylic acid bisimide (20 mg) was used, the same procedure as in Example 3 was performed. A purple organic silica thin film comprising a perylene bisimide skeleton-containing Si polymer / surfactant was obtained.

  FIG. 7 shows an X-ray diffraction pattern of the obtained thin film, and FIG. 8 shows an ultraviolet / visible absorption spectrum. This organic silica thin film was confirmed to have a mesostructure with a period of 5.1 nm. It was also confirmed that it has an absorption maximum near a wavelength of 590 nm, and the absorption edge on the long wavelength side of the absorption spectrum is 650 nm or more.

(Example 8)
A perylene bisimide skeleton-containing Si-based porous material as in Example 4 except that an organic silica thin film prepared in the same manner as in Example 7 was used instead of the organic silica thin film prepared in the same manner as in Example 3. A thin film was obtained.

  An X-ray diffraction pattern of the obtained porous thin film is shown in FIG. 7, and an ultraviolet / visible absorption spectrum is shown in FIG. This porous thin film was confirmed to have a mesoporous structure with a period of 6.7 nm. It was also confirmed that it has an absorption maximum near a wavelength of 590 nm, and the absorption edge on the long wavelength side of the absorption spectrum is 650 nm or more.

(Comparative Example 1)
<Preparation of organosilica composed of perylene bisimide skeleton-containing Si polymer / surfactant>
Tetrahydrofuran (1.2 mL), nonionic surfactant Brij76 (10 mg) N, N′-bis [4- (triethoxysilyl) phenyl] -perylene-3,4: 9,10-tetra obtained in Synthesis Example 3 Carboxylic acid bisimide (15 mg), water (6 μL) and 2 mol / L hydrochloric acid (2 μL) were mixed to prepare a homogeneous solution, which was stirred at room temperature, and a red precipitate was formed in about 2 hours. This precipitate was collected by suction filtration to obtain organic silica composed of a perylene bisimide skeleton-containing Si polymer / surfactant.

  The X-ray diffraction pattern of the obtained organic silica is shown in FIG. In this organosilica, no diffraction peak in the low angle region indicating the formation of a mesostructure was observed.

  As is apparent from the results shown in FIGS. 1 to 9, the organosilica material of the present invention using an organosilane compound having a perylene bisimide skeleton having at least three alkoxysilyl groups and a surfactant (Example 1) 3, 5, 7) and the organic silica-based porous material (Examples 2, 4, 6, 8) obtained by removing the surfactant from the organic silica-based material have a mesostructure, and It was confirmed that the absorption wavelength on the long wavelength side of the absorption spectrum is at least 600 nm, that is, absorbs light having a wavelength of 600 nm or more.

  On the other hand, in the case of using an organosilane compound having a perylene bisimide skeleton having two alkoxysilyl groups and a surfactant (Comparative Example 1), it was confirmed that no mesostructure was formed in the organic silica material. .

  As described above, according to the present invention, an organic silica mesostructure and an organic silica mesoporous body having a perylene bisimide skeleton can be obtained. In particular, an organic silica-based mesostructure and an organic silica-based mesoporous material having an absorption edge on the long wavelength side of the absorption spectrum of 600 nm or more can be obtained.

  Therefore, since the organic silica-based material and the organic silica-based mesoporous material of the present invention can absorb at least light having a wavelength of 600 nm or more, they can efficiently absorb visible light having a wavelength of 500 nm or more. Furthermore, since it has a mesostructure, it is useful as a visible light responsive photocatalyst or photoelectric conversion element that can utilize sunlight.

Claims (6)

Following formula (1):

[In the formula (1), at least three groups of R ^{1 to} R ¹⁰ are each independently represented by the following formula (2):
_{^{- (Z) m -Si (OR}} a) n R b 3-n (2)
(In formula (2), R ^a represents an alkyl group having 1 to 8 carbon atoms, R ^b represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group having 2 to 8 carbon atoms, and Z Is selected from the group consisting of alkylene groups having 1 to 12 carbon atoms, arylene groups having 6 to 12 carbon atoms, ethenylene groups, ethynylene groups, ether groups, carbonyl groups, amino groups, amide groups, urethane groups and imide groups. 1 type of group is represented, m is an integer of 0-2, n is an integer of 1-3.)
A substituent containing an alkoxysilyl group represented by:
Groups other than the substituent containing the alkoxysilyl group among R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, One group selected from the group consisting of an aryl group having 6 to 12 carbon atoms, a phenoxy group, an acetyl group, a benzoyl group, an amino group, an amide group, a nitro group, a cyano group, and an imide group;
The groups other than the substituent containing the alkoxysilyl group among R ^{9 to} R ¹⁰ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. One kind of group selected. ]
An organosilica-based material comprising a polymer having a mesostructure of a perylene-based organosilane compound represented by the formula: and a surfactant. Organic according to claim 1, characterized in that it is a substituent containing an alkoxysilyl group, wherein R ^2, R 3 of formula (1) ^in, R ⁶ and R ⁷ is represented by the formula (2) Silica-based material.   The organic silica-based material according to claim 1 or 2, wherein the wavelength of the absorption edge on the long wavelength side of the absorption spectrum is 600 nm or more. Following formula (1):

[In the formula (1), at least three groups of R ^{1 to} R ¹⁰ are each independently represented by the following formula (2):
_{^{- (Z) m -Si (OR}} a) n R b 3-n (2)
(In formula (2), R ^a represents an alkyl group having 1 to 8 carbon atoms, R ^b represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group having 2 to 8 carbon atoms, and Z Is selected from the group consisting of alkylene groups having 1 to 12 carbon atoms, arylene groups having 6 to 12 carbon atoms, ethenylene groups, ethynylene groups, ether groups, carbonyl groups, amino groups, amide groups, urethane groups and imide groups. 1 type of group is represented, m is an integer of 0-2, n is an integer of 1-3.)
A substituent containing an alkoxysilyl group represented by:
Groups other than the substituent containing the alkoxysilyl group among R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, One group selected from the group consisting of an aryl group having 6 to 12 carbon atoms, a phenoxy group, an acetyl group, a benzoyl group, an amino group, an amide group, a nitro group, a cyano group, and an imide group;
The groups other than the substituent containing the alkoxysilyl group among R ^{9 to} R ¹⁰ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. One kind of group selected. ]
An organosilica mesoporous material comprising a polymer of a perylene-based organosilane compound represented by the formula: 5. The organic according to claim 4, wherein R ² , R ³ , R ⁶ and R ⁷ in the formula (1) are a substituent containing an alkoxysilyl group represented by the formula (2). Silica-based mesoporous material.   6. The organosilica-based mesoporous material according to claim 4 or 5, wherein the wavelength at the absorption edge on the long wavelength side of the absorption spectrum is 600 nm or more.

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