JP2013189603A - Organic silica-based material - Google Patents

Abstract

〔式（１）中のＲ^１〜Ｒ^３のうちの少なくとも１つの基およびＲ^４〜Ｒ^６のうちの少なくとも１つの基は、−Ｚ−Ｓｉ（Ｒａ）３−ｉ−ｊ（ＯＨ）ｊ−（（Ｏ）０．５）ｉ−で表される基（Ｚは、アリーレン基、複素環基、エテニレン基、エチニレン基、エーテル基、カルボニル基、アミノ基、アミド基、イミド基、単結合などを表し、Ｒ^ａはアルキル基またはアリル基を表す）〕を有することを特徴とする有機シリカ系材料。
【選択図】なしA material having visible light absorption characteristics and high durability against oxygen and heat is provided.
A repeating unit represented by the following formula (1):

[In formula (1), at least one group of R ^{1 to} R ³ and at least one group of R ^{4 to} R ⁶ are each represented by —Z—Si (Ra) 3-i-j (OH) j A group represented by-((O) 0.5) i- (Z is an arylene group, heterocyclic group, ethenylene group, ethynylene group, ether group, carbonyl group, amino group, amide group, imide group, single bond And R ^a represents an alkyl group or an allyl group)].
[Selection figure] None

Description

  The present invention relates to an organic silica-based material, and more particularly to an organic silica-based material having a dithienyl diketopyrrolopyrrole skeleton.

  Diketopyrrolopyrrole compounds are conventionally used as sensitizing dyes in photoelectric conversion materials. Also, Adv. Mater. 2010, Vol. 22, pp. E242 to E246 (Non-Patent Document 1) discloses a polymer material in which dithienyl diketopyrrolopyrrole skeletons and phenylene groups are alternately bonded. It is also disclosed that the resulting organic thin film can absorb visible light of 500 nm or more.

  However, a polymer material in which a dithienyl diketopyrrolopyrrole skeleton and a phenylene group are alternately bonded has a problem that it is easily decomposed by heat and oxidatively and is easily modified by heat and oxygen.

Johan C.H. Bijlevel et al., Adv. Mater. 2010, Vol. 22, pp. E242-E246

  The present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide a material having visible light absorption characteristics and high durability against oxygen and heat.

  As a result of intensive studies to achieve the above object, the present inventors have cross-linked a dithienyl diketopyrrolopyrrole skeleton (hereinafter abbreviated as “DPP skeleton”) three-dimensionally with a siloxane bond, It has been found that an organic silica material having visible light absorption characteristics and high durability against oxygen and heat can be obtained, and the present invention has been completed.

  That is, the organic silica material of the present invention is a repeating unit represented by the following formula (1):

[At least one group of R ^{1 to} R ³ and at least one group of R ^{4 to} R ^{6 in} the formula (1) are each independently a group represented by the following formula (2):

(In the formula (2), Z represents an arylene group having 6 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, an ethenylene group, an ethynylene group, an ether group, a carbonyl group, an amino group, an amide group, and an imide group. A group containing at least one selected from the group consisting of a single bond, R ^a represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group, k is 1 or 2, and i is An integer of 1 to 3, j is an integer of 0 to 2, 1 ≦ i + j ≦ 3, and a plurality of combinations of i and j are independent of each other in the group represented by the formula (2). And * is a binding site with an adjacent repeating unit.)
In the formula (1), the remaining groups of R ^{1 to} R ⁶ and R ^{7 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a phenoxy group, acetyl It is one selected from the group consisting of a group, a benzoyl group, an amino group, an amide group, an imide group, a nitro group, and a cyano group. ]
It is characterized by having.

In the organosilica-based material of the present invention, Z in the formula (2) is preferably a group containing an arylene group having 6 to 20 carbon atoms that does not contain an aromatic condensed ring, and a monocyclic aromatic ring and an alkylene group. And a group in which and are bonded is more preferred. In addition, as the organic silica material of the present invention, it is preferable that R ¹ and R ⁴ in the formula (1) are groups represented by the formula (2).

  The reason why the organosilica material of the present invention exhibits high durability against oxygen and heat is not necessarily clear, but the present inventors speculate as follows. That is, in a conventional polymer material having a DPP skeleton, the DPP skeleton is connected by a carbon-carbon bond, and this carbon-carbon bond is cut by heat or oxygen, so that it has high durability against heat and oxygen. It is presumed that it was difficult to form a polymer material exhibiting properties.

  On the other hand, in the organic silica-based material of the present invention, since the DPP skeleton is three-dimensionally cross-linked by a siloxane bond (Si—O bond), the bond breakage due to heat and oxygen hardly occurs. It is presumed that it exhibits high durability.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to obtain the organic silica type material which has a visible light absorption characteristic and shows high durability with respect to oxygen and a heat | fever.

It is a graph which shows the visible / ultraviolet absorption spectrum before and behind the heating of the organic silica type thin film (DPP-2SiP) obtained in Example 1. It is a graph which shows the visible / ultraviolet absorption spectrum before and behind the heating of the organic silica type thin film (DPP-4SiP) obtained in Example 2. It is a graph which shows the visible / ultraviolet absorption spectrum before and behind the heating of the polymer thin film (pDPP-Ph) obtained in Comparative Example 1. It is a graph which shows the absorption spectrum which normalized the visible / ultraviolet absorption spectrum of the polymer thin film (pDPP-Ph) obtained in Comparative Example 1 with the absorbance at the maximum absorption maximum wavelength.

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

  The organosilica-based material of the present invention is a repeating unit represented by the following formula (1):

[At least one group of R ^{1 to} R ³ and at least one group of R ^{4 to} R ^{6 in} the formula (1) are each independently a group represented by the following formula (2):

In the formula (1), the remaining groups of R ^{1 to} R ⁶ and R ^{7 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a phenoxy group, acetyl It is one selected from the group consisting of a group, a benzoyl group, an amino group, an amide group, an imide group, a nitro group, and a cyano group. ]
It is what has.

  Since the organic silica material of the present invention has such a DPP skeleton, the wavelength of the absorption edge on the long wavelength side of the absorption spectrum becomes 600 nm or more, and can efficiently absorb visible light of 500 nm or more. It becomes possible. Further, the group represented by the formula (2) is a group having a crosslinking point (hereinafter referred to as “crosslinking group”), and the DPP skeleton is three-dimensionally formed by a siloxane bond (Si—O bond) in the crosslinking group. Therefore, the bond is not easily broken by heat or oxygen, and exhibits high durability against heat and oxygen.

In the repeating unit represented by the formula (1), at least one group of R ^{1 to} R ³ and at least one group of R ^{4 to} R ^{6 in} the formula (1) are each independently Although it is a crosslinking group represented by the formula (2), R ¹ and R ⁴ may be the crosslinking group from the viewpoint that it is easy to synthesize an organosilane compound that is a raw material of the organic silica material of the present invention. preferable.

  Z in the formula (2) is an arylene group having 6 to 20 carbon atoms (preferably 6 to 15), a heterocyclic group having 2 to 20 carbon atoms (preferably 4 to 15), an ethenylene group, an ethynylene group, an ether. A group having at least one selected from the group consisting of a group, a carbonyl group, an amino group, an amide group and an imide group, preferably a k-valent or higher group (preferably a k + 1-valent group) or a single bond.

  Examples of the arylene group include monocyclic aromatic rings such as a phenylene group; aromatic condensed rings such as a naphthylene group and a fluorenylene group. Examples of the heterocyclic group include a sulfur-containing five-membered ring such as a thienylene group; a nitrogen-containing aromatic ring such as a pyridylene group; and a nitrogen-containing condensed ring such as a carbazolylene group.

  Among these groups, Z in the formula (2) is preferably a group not containing an aromatic condensed ring from the viewpoint of chemical stability, and is preferably a monocyclic aromatic ring (more preferably a phenylene group), A group containing an ethenylene group, an ethynylene group, an ether group, or an amino group and not containing an aromatic condensed ring is more preferable.

  Further, when a plurality of the predetermined groups are contained in Z in the formula (2), they may be the same group or different groups. Z containing the same kind of group includes a k-valent or higher group having a biphenyl skeleton (preferably a divalent group), a k-valent or higher group having a triphenylamine skeleton (preferably a divalent or trivalent group). ) And the like. In addition, as Z containing different groups, an arylene group (preferably a monocyclic aromatic ring, more preferably a phenylene group) and an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). And a group having a valence of at least k (preferably a divalent group).

^Ra in the formula (2) represents an alkyl group or an allyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms), and the allyl group may have a substituent such as a methyl group. * Is a binding site with an adjacent repeating unit. In the formula (2), k is 1 or 2, i is an integer of 1 to 3, j is an integer of 0 to 2, and 1 ≦ i + j ≦ 3. Note that the combination of i and j is independent for each of the plurality of cross-linking groups, and need not be the same for all the cross-linking groups in the organic silica material.

In the repeating unit represented by the formula (1), a group other than the remaining group of R ^{1 to} R ⁶ and R ^{7 to} R ⁸ , that is, a group containing a silyl group represented by the formula (2). Each group is independently a hydrogen atom, a halogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), or an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 carbon atom). -6), an aryl group (preferably having 6 to 12 carbon atoms), a phenoxy group, an acetyl group, a benzoyl group, an amino group, an amide group, an imide group, a nitro group, and a cyano group. is there. Among these groups, the remaining groups of R ^{1 to} R ⁶ include a hydrogen atom, a methyl group, an ethyl group, from the viewpoint of chemical stability and high density of the DPP skeleton in the organic silica-based material. A methoxy group, a phenyl group, and a phenoxy group are preferable, and R ^{7 to} R ⁸ are preferably a 2-ethylhexyl group.

Among such organic silica-based materials, from the viewpoint of reducing the volume fraction of the organic skeleton with respect to the cross-linking group and achieving a high light absorption rate (particularly visible light absorption rate), in the formula (1) Any one group of R ^{1 to} R ³ (more preferably R ¹ ) and any one group of R ^{4 to} R ⁶ (more preferably R ⁴ ) is represented by the formula (2). The remaining groups of R ^{1 to} R ⁶ and R ^{7 to} R ⁸ are hydrogen atoms, and Z in the formula (2) is a monocyclic aromatic ring (more preferably a phenylene group). An organic silica-based material that is a group in which an alkylene group is bonded is preferable.

  The organosilica-based material of the present invention includes, for example, the following formula (1a):

[At least one group of R ^{1 to} R ³ and at least one group of R ^{4 to} R ^{6 in} the formula (1a) are each independently represented by the following formula (2a):

Wherein the remaining groups of R ^{1 to} R ⁶ and R ^{7 to} R ⁸ in the formula (1a) are R ¹ to R ¹ in the formula (1). is synonymous with groups other than the crosslinking group represented by the remaining groups and R ⁷ above formula is to R ⁸ (2) of the R ^6. ]
It can manufacture by hydrolyzing and polycondensing the organosilane compound which has DPP frame | skeleton represented by these.

Z in formula (2a), ^{R a} and k, Z in the formula (2) have the same meanings as ^{R a} and k. In the formula (2a), R ^b represents an alkyl group having 1 to 8 (preferably 1 to 4) carbon atoms, and among them, a methyl group, an ethyl group, and an isopropyl group are more preferable. n is an integer of 0-3. When R ^a is an allyl group, the allyl group is eliminated by hydrolysis. Therefore, the value of (3-n) in the formula (2a) and (3-i-j) in the formula (2) are used. The values of do not necessarily match.

When producing the organic silica material of the present invention, such an organic silane compound having a DPP skeleton may be used alone or in combination of two or more. Moreover, among the organic silane compounds having such a DPP skeleton, the substituent represented by the formula (2a) is easily introduced, and in the obtained organic silica material, the volume of the organic skeleton with respect to the crosslinking group From the viewpoint of reducing the rate and achieving a high light absorption rate (particularly visible light absorption rate), any one group of R ^{1 to} R ³ in the formula (1a) (more preferably R ¹ ) And R ^{4 to} R ⁶ (more preferably R ⁴ ) is a group represented by the formula (2a), and the remaining groups of R ^{1 to} R ⁶ and R ⁷ to R ⁸ is a hydrogen atom, the formula Z in (2a) is a monocyclic aromatic ring (more preferably a phenylene group) and an alkylene group (more preferably 1 to 12 carbon atoms, particularly preferably 1 carbon atoms Organosilane compound which is a group to which -6) is bonded Things are preferred. Moreover, from a viewpoint that an organosilane compound is easy to hydrolyze and polycondensate, as ^Rb in the said Formula (2a), a C1-C2 alkyl group is preferable. Furthermore, n in the formula (2a) is preferably 2 or 3, and particularly preferably 3, from the viewpoint that the degree of crosslinking of the obtained organic silica-based material can be increased and the structure can be stabilized.

  Examples of such an organosilane compound having a DPP skeleton are Maegawa Y. et al. Etal., Tetrahedron, 2007, Vol. 63, p. 11467-11474, etc., and halogenated dithienyl diketopyrrolopyrroles substituted with at least one halogen atom on each thienyl skeleton, and halogen atoms. It can be produced by reacting a functional group capable of reacting with a silane compound containing a silyl group capable of hydrolysis and polycondensation. Examples of the halogenated dithienyl diketopyrrolopyrroles include, for example, Tamayo A. et al. B. Et al. Phys. Chem. C, 2008, 112, 15543-15552, and the like. Silane compounds containing a functional group capable of reacting with the halogen atom and a silyl group capable of hydrolysis and polycondensation are disclosed in, for example, Japanese Patent Application Laid-Open No. 2008-214314 and Maegawa Y. et al. Et al., Tetrahedron, 2007, Vol. 63, pages 11467-11474, and the like.

  Moreover, when manufacturing the organic silica type material of this invention, you may copolymerize the organic silane compound which has the said DPP frame | skeleton, and another organic silane compound. 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. The proportion of the other organic silane compound is preferably 90 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 10 parts by mass or less with respect to 100 parts by mass of the organic silane compound having the DPP skeleton.

  The conditions for the hydrolysis / polycondensation (including copolymerization) are not particularly limited, but it is preferable to hydrolyze and polycondensate the silane monomer in a solvent in the presence of an acid or base catalyst. Examples of the solvent used at this time include alcohol, tetrahydrofuran, an organic solvent of acetone, water, and a mixed solvent thereof. Although there is no restriction | limiting in particular as a density | concentration of the said silane monomer in a solution, 0.05-5 mass% is preferable.

  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.

  Various conditions (temperature, time, etc.) in the hydrolysis / polycondensation (including copolymerization) are not particularly limited and are appropriately selected according to the silane monomer used, the target organic silica material, etc. The silane monomer can be hydrolyzed and polycondensed at a temperature of about 0 to 150 ° C. for a time of about 30 minutes to 48 hours.

  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. For example, when producing a thin-film organic silica-based material, first, an acid (for example, hydrochloric acid or nitric acid) is added to a solution containing the silane monomer (for example, tetrahydrofuran solution), and this solution is stirred to partially A sol solution containing the partial polymer is produced by a reaction (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. In addition, the reaction temperature is preferably about 0 to 100 ° C., and the reaction time is preferably about 30 minutes to 24 hours.

  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 that the obtained thin film is dried at about 25 to 120 ° C., and the polycondensation reaction of the partial polymer is advanced to form a three-dimensional crosslinked structure. Although there is no restriction | limiting in particular as an average film thickness of the thin film obtained, 100 micrometers or less are preferable and 0.01-10 micrometers is more preferable. Such a thin-film organic silica-based material can also be obtained in accordance with a method described in JP-A No. 2001-130911.

  Thus, when the organosilane compound having the DPP skeleton is hydrolyzed and polycondensed, the silyl group in the formula (2a) is usually hydrolyzed to form a silanol group (Si—OH), and then Siloxane bonds (Si—O—Si) are formed by the condensation polymerization reaction. At this time, a part of the silanol group is not converted to a siloxane bond and remains as it is, or even if the allyl group bonded to Si remains as it is, the light absorption characteristics of the organosilica material of the present invention (particularly, Visible light absorption characteristics) are not significantly affected.

  In the production of the organic silica-based material of the present invention, the silane monomer is hydrolyzed and polycondensed in the presence of a surfactant, thereby having a DPP skeleton and a central pore diameter in a pore size distribution curve. It is also possible to produce an organic silica-based mesoporous material having a structure (mesostructure) having mesopores of 1 to 30 nm. Specifically, a mesoporous material precursor containing the organosilica material of the present invention and a surfactant is prepared by the hydrolysis and polycondensation, and the surfactant is removed from the mesoporous material precursor. By this, an organosilica mesoporous material can be obtained.

  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.

(Synthesis Example 1)
<Synthesis of 1-iodo-4- (3- (triisopropoxysilyl) propyl) benzene>
First, 1-allyl-4-iodobenzene (6.53 g, 26.8 mmol) and di-μ-chlorodichlorobis (ethylene) diplatinum (II) (2.0 mg, 3.4 μmol, Pt content: 0.025 mol) %) And trichlorosilane (10 ml, 99.0 mmol) was added dropwise at 0 ° C. under an argon atmosphere. The resulting solution was stirred at 0 ° C. for 10 minutes, then stirred at room temperature for an additional 18 hours, and the following reaction formula (I):

The reaction represented by The solution after the reaction a small amount collected, was dissolved in dehydrated ^chloroform-1 disappeared and 1-iodo-4-1-allyl-4-iodobenzene by H-NMR measurement (3- (trichlorosilyl) propyl) benzene Confirmed the generation of. Thereafter, an excess amount of trichlorosilane was distilled off from the solution after the reaction under reduced pressure.

  Next, the obtained 1-iodo-4- (3- (trichlorosilyl) propyl) benzene was redissolved in dehydrated dichloromethane (40 ml) and then cooled to 0 ° C. dehydrated 2-propanol (10.0 ml, 130 mmol). And anhydrous pyridine (10.5 ml, 130 mmol) were slowly added dropwise to a dehydrated dichloromethane (100 ml) solution. The resulting solution was stirred at room temperature for 5 hours, and the following reaction formula (II):

The reaction represented by Thereafter, the solvent was distilled off from the solution after the reaction under reduced pressure, the resulting inorganic salt was removed by Celite filtration, and the residue was further washed with hexane. The obtained organic layer was concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10/1) to obtain a colorless and transparent liquid (yield 10.3 g, yield 86%).

This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and confirmed to be 1-iodo-4- (3- (triisopropoxysilyl) propyl) benzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.57-0.61 (m, 2H), 1.17 (d, J = 6.4 Hz, 18H), 1.57-1.73 (m, 2H) ), 2.57 (t, J = 7.6 Hz, 2H), 4.18 (sept, J = 6.4 Hz, 3H), 6.92 (d, J = 8.4 Hz, 2H), 7.57 (D, J = 8.4 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 11.6, 24.9, 25.6, 38.7, 64.9, 90.5, 130.7, 137.2, 142.2.

<Synthesis of 4- (3- (triisopropoxysilyl) propyl) -1-trimethylstannylbenzene>
1-Iodo-4- (3- (triisopropoxysilyl) propyl) benzene (1.03 g, 2.29 mmol) was dissolved in dehydrated tetrahydrofuran (THF, 18 ml), and the resulting solution was cooled to 0 ° C. In an argon atmosphere, isopropylmagnesium chloride (5.17 ml, 10.3 mmol) was added dropwise as a tetrahydrofuran solution (concentration: 2.0 mol / L). The resulting solution was stirred at room temperature for 4 hours, and the following reaction formula (III):

A 4- (3- (triisopropoxysilyl) propyl) phenylmagnesium chloride solution was obtained.

  The 4- (3- (triisopropoxysilyl) propyl) phenylmagnesium chloride solution was cooled to −78 ° C., then trimethine tin chloride (2.05 g, 10.3 mmol) was added all at once, and the mixture was stirred at room temperature for 17 hours. The following reaction formula (IV):

The reaction was stopped by adding the resulting solution to a saturated aqueous ammonium chloride solution cooled to 0 ° C. After the organic layer and the aqueous layer were separated, the aqueous layer was extracted with diethyl ether. The obtained organic layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10/1) to obtain a colorless and transparent liquid (yield 965 mg, yield 87%).

This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and confirmed to be 4- (3- (triisopropoxysilyl) propyl) -1-trimethylstannylbenzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.27 (t, J = 27.6 Hz, 9H), 0.62-0.66 (m, 2H), 1.18 (d, J = 6.4 Hz) , 18H), 1.69-1.76 (m, 2H), 2.61 (t, J = 8.0 Hz, 2H), 4.19 (sept, J = 6.4 Hz, 3H), 7.17. (D, J = 7.6 Hz, 2H), 7.40 (d, J = 7.6 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ-9.6, 11.9, 25.1, 25.6, 39.4, 64.8, 128.4, 135.7, 138.6, 142 .7.

<3,6-bis (5- (4- (triisopropoxysilyl) propyl) phenylthiophen-2-yl) -2,5-bis (2-ethylhexyl) pyrrolo [3,4-c] pyrrole-1, Synthesis of 4-dione>
3,6-bis (5-bromothiophen-2-yl) -2,5-bis (2-ethylhexyl) pyrrolo [3,4-c] pyrrole-1,4-dione (198 mg, 0.29 mmol), 4 -(3- (triisopropoxysilyl) propyl) -1-trimethylstannylbenzene (420 mg, 0.86 mol), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ , 13.3 mg, 0.015 mmol, Pd content: 10 mol%) and tri (2-furyl) phosphine (TFP, 14.6 mg, 0.058 mmol, 20 mol%) were mixed, and the resulting mixture was mixed with dehydrated tetrahydrofuran (30 ml) under an argon atmosphere. ) Was added. The resulting solution was stirred at 70 ° C. for 20 hours, and the following reaction formula (V):

The reaction represented by Thereafter, the solvent was distilled off from the solution after the reaction under reduced pressure to obtain a crude product. This crude product was purified by silica gel column chromatography (developing solvent: hexane / chloroform = 1/1) and flash column chromatography (developing solvent: hexane / ethyl acetate = 40/1) to give a dark blue solid (yield 289 mg, Yield 85%).

This dark blue solid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and 3,6-bis (5- (4- (triisopropoxysilyl) propyl) phenylthiophen-2-yl) -2,5 -It was confirmed that it was bis (2-ethylhexyl) pyrrolo [3,4-c] pyrrole-1,4-dione (DPP-2SiP). The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.62-0.66 (m, 4H), 0.87 (t, J = 6.8 Hz, 6H), 0.91 (t, J = 7.2 Hz) 6H) 1.19 (d, J = 6.4 Hz, 36H), 1.24-1.42 (m, 16H), 1.72-1.80 (m, 4H), 1.90-2. 00 (m, 2H), 2.67 (t, J = 7.6 Hz, 4H), 4.03-4.13 (m, 4H), 4.20 (sept, J = 6.4 Hz, 6H), 7.23 (d, J = 8.4 Hz, 4H), 7.42 (d, J = 4.0 Hz, 2H), 7.58 (d, J = 8.4 Hz, 4H), 8.96 (d , J = 4.0 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 10.6, 11.8, 14.1, 23.1, 23.7, 25.0, 25.6, 28.6, 30.4, 39.0 39.2, 46.0, 64.9, 108.0, 124.0, 126.0, 128.3, 129.3, 130.7, 136.8, 139.8, 143.8, 150 0.0, 161.7.

(Synthesis Example 2)
<Synthesis of 1-allyl-3,5-dibromobenzene>
First, a dehydrated cyclopentylmethyl ether (CPME, 120 ml) solution of 1,3,5-tribromobenzene (25.4 g, 80.7 mmol) was cooled to −5 ° C., and then isopropylmagnesium chloride (16. 2 ml, 32.4 mmol) was added dropwise as a tetrahydrofuran solution (concentration: 2.0 mol / L), and n-butyllithium (25.8 ml, 64.5 mmol) was added dropwise as a hexane solution (concentration: 2.5 mol / L). The resulting solution was stirred at −5 ° C. for 8 hours, and the following reaction formula (VI):

Was carried out to obtain a 3,5-dibromophenylmagnesium chloride solution.

  To this 3,5-dibromophenylmagnesium chloride solution, copper (I) cyanide (723 mg, 8.0 mmol, 10 mol%) was added at once and stirred at −5 ° C. for 5 minutes, after which allyl bromide (10.2 ml, 120.6 mmol) was added dropwise at −5 ° C., and the mixture was stirred at room temperature for 15 hours. The following reaction formula (VII):

The generated inorganic salt was removed by Celite filtration, and the resulting solution was added to a saturated aqueous ammonium chloride solution cooled to 0 ° C. to stop the reaction. After the organic layer and the aqueous layer were separated, the aqueous layer was extracted with diethyl ether. The obtained organic layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and concentrated to obtain an almost pure brown transparent liquid (yield 21.4 g, yield 96%).

This brown transparent liquid was identified by ¹ H-NMR measurement and confirmed to be 1-allyl-3,5-dibromobenzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 3.33 (d, J = 6.8 Hz, 2H), 5.08-5.15 (m, 2H), 5.83-5.94 (m, 1H) ), 7.27 (d, J = 1.6 Hz, 2H), 7.50 (t, J = 1.6 Hz, 1H).

<Synthesis of 1-bromo-3,5-diallylbenzene>
1-allyl-3,5-dibromobenzene (21.4 g, 77.5 mmol) was dissolved in dehydrated cyclopentylmethyl ether (100 ml), and the resulting solution was cooled to −5 ° C. and then isopropylmagnesium under an argon atmosphere. Chloride (16.2 ml, 32.4 mmol) as a tetrahydrofuran solution (concentration: 2.0 mol / L) and n-butyllithium (25.8 ml, 64.5 mmol) as a hexane solution (concentration: 2.5 mol / L) It was dripped. The resulting solution was stirred at −5 ° C. for 8 hours, and the following reaction formula (VIII):

A 3-allyl-5-bromophenylmagnesium chloride solution was obtained.

  To this 3-allyl-5-bromophenylmagnesium chloride solution was added copper (I) cyanide (705 mg, 7.8 mmol, 10 mol%) at a time, and the mixture was stirred at −5 ° C. for 5 minutes, and then allyl bromide (10.2 ml). , 120.6 mmol) was added dropwise at −5 ° C. and stirred at room temperature for 15 hours, and the following reaction formula (IX):

The generated inorganic salt was removed by Celite filtration, and the resulting solution was added to a saturated aqueous ammonium chloride solution cooled to 0 ° C. to stop the reaction. After the organic layer and the aqueous layer were separated, the aqueous layer was extracted with diethyl ether. The obtained organic layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and concentrated to obtain a crude product. The crude product was purified by distillation under reduced pressure (150 Pa, 100 ° C.) to obtain a colorless and transparent liquid (yield 17.5 g, yield 96%).

This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and confirmed to be 1-bromo-3,5-diallylbenzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 3.33 (d, J = 6.8 Hz, 4H), 5.05 to 5.11 (m, 4H), 5.86-5.96 (m, 2H) ), 6.92 (s, 1H), 7.25 (s, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 39.8, 116.5, 122.4, 127.7, 129.3, 136.5, 142.3.

<Synthesis of 1,3-diallyl-5-iodobenzene>
1-Bromo-3,5-diallylbenzene (4.74 g, 20.0 mmol) was dissolved in dehydrated cyclopentylmethyl ether (20 ml), and the resulting solution was cooled to 0 ° C. and then isopropylmagnesium chloride under an argon atmosphere. (6.6 ml, 13.2 mmol) as a tetrahydrofuran solution (concentration: 2.0 mol / L) and n-butyllithium (10.6 ml, 26.5 mmol) as a hexane solution (concentration: 2.5 mol / L) was added dropwise. did. The resulting solution was stirred at 0 ° C. for 6 hours, and the following reaction formula (X):

A 1,3-diallylphenylmagnesium chloride solution was obtained.

  To this 1,3-diallylphenylmagnesium chloride solution, a dehydrated tetrahydrofuran solution (40 ml) of iodine (11.0 g, 43.3 mmol) was added dropwise and stirred at room temperature for 13 hours. The following reaction formula (XI):

The reaction was stopped by adding the resulting solution to a saturated aqueous ammonium chloride solution cooled to 0 ° C. After the organic layer and the aqueous layer were separated, the aqueous layer was extracted with diethyl ether. The obtained organic layer was washed with a saturated aqueous sodium thiosulfate solution and a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and concentrated to obtain a crude product. The crude product was purified by distillation under reduced pressure (200 Pa, 110 ° C.) to obtain a colorless and transparent liquid (yield 4.36 g, yield 77%).

This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and confirmed to be 1,3-diallyl-5-iodobenzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 3.30 (d, J = 6.8 Hz, 4H), 5.05 to 5.11 (m, 4H), 5.85-5.95 (m, 2H) ), 6.96 (s, 1H), 7.38 (d, J = 1.2 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 39.6, 94.6, 116.4, 128.3, 135.3, 136.5, 142.4.

<Synthesis of 1,3-bis (3- (triisopropoxysilyl) propyl) -5-iodobenzene>
1,3-diallyl-5-iodobenzene (4.5 g, 15.8 mmol) was dissolved in a mixed solution of dehydrated diethyl ether (12 ml) / dehydrated dichloromethane (15 ml), and hexachlorochloromethane was dissolved in the resulting solution under an argon atmosphere. A dehydrated dichloromethane solution (3 ml) of platinum acid (IV) tetrabutylammonium (14.1 mg, 15.8 μmol, Pt content: 0.1 mol%) was added, and trichlorosilane (7.5 ml, 74.3 mmol) was added at 0 ° C. It was dripped. The resulting solution was stirred at 0 ° C. for 10 minutes, and further stirred at room temperature for 15 hours to obtain the following reaction formula (XII):

The reaction represented by A small amount of the solution after the reaction was collected and dissolved in dehydrated deuterated chloroform, and then disappearance of 1,3-diallyl-5-iodobenzene and 1,3-bis (3- (trichlorosilyl) propyl) were determined by ¹ H-NMR measurement. Formation of -5-iodobenzene was confirmed. Thereafter, an excess amount of trichlorosilane was distilled off from the solution after the reaction under reduced pressure.

  Next, the obtained 1,3-bis (3- (trichlorosilyl) propyl) -5-iodobenzene was redissolved in dehydrated dichloromethane (75 ml), and then dehydrated 2-propanol (13.0 ml) cooled to 0 ° C. , 170 mmol) and dehydrated dichloromethane (150 ml) containing dehydrated pyridine (14.0 ml, 170 mmol). The resulting solution was stirred at room temperature for 3 hours, and the following reaction formula (XIII):

The reaction represented by Thereafter, the solvent was distilled off from the solution after the reaction under reduced pressure, the resulting inorganic salt was removed by Celite filtration, and the residue was further washed with hexane. The obtained organic layer was concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10/1) to obtain a colorless and transparent liquid (yield 9.27 g, yield 84%).

This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and confirmed to be 1,3-bis (3- (triisopropoxysilyl) propyl) -5-iodobenzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.57-0.62 (m, 4H), 1.18 (d, J = 6.0 Hz, 36H), 1.64-1.72 (m, 4H) ), 2.53 (t, J = 7.6 Hz, 4H), 4.19 (sept, J = 6.0 Hz, 6H), 6.92 (s, 2H), 7.33 (s, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 11.7, 24.9, 25.6, 38.8, 64.9, 94.3, 128.3, 134.8, 144.7.

<Synthesis of 1,3-bis (3- (triisopropoxysilyl) propyl) -5- (trimethylstannyl) benzene>
1,3-bis (3- (triisopropoxysilyl) propyl) -5-iodobenzene (340 mg, 0.49 mmol) was dissolved in dehydrated tetrahydrofuran (3 ml), and the resulting solution was cooled to 0 ° C. Isopropylmagnesium chloride (2.0 ml, 4.00 mmol) was added dropwise as a tetrahydrofuran solution (concentration: 2.0 mol / L) under an argon atmosphere. The resulting solution was stirred at room temperature for 6 hours, and the following reaction formula (XIV):

To obtain a 1,3-bis (3- (triisopropoxysilyl) propyl) phenylmagnesium chloride solution.

  Trimethyltin chloride (797 mg, 4.00 mmol) was added to the 1,3-bis (3- (triisopropoxysilyl) propyl) phenylmagnesium chloride solution all at once, and the mixture was stirred at room temperature for 17 hours. ):

The reaction was stopped by adding the resulting solution to a saturated aqueous ammonium chloride solution cooled to 0 ° C. After the organic layer and the aqueous layer were separated, the aqueous layer was extracted with diethyl ether. The obtained organic layer was washed with a saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate, filtered and concentrated to obtain an almost pure colorless transparent liquid (yield 341 mg, yield 95%).

This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and was found to be 1,3-bis (3- (triisopropoxysilyl) propyl) -5- (trimethylstannyl) benzene. confirmed. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.26 (t, J = 28.0 Hz, 9H), 0.63-0.67 (m, 4H), 1.18 (d, J = 6.4 Hz) 36H), 1.66-1.76 (m, 4H), 2.59 (t, J = 8.0 Hz, 4H), 4.91 (sept, J = 6.4 Hz, 6H), 6.93. (S, 1H), 7.10 (d, J = 1.2 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ-9.6, 12.0, 25.2, 25.6, 39.5, 64.8, 128.9, 133.3, 141.5, 142 0.0.

<3,6-bis (5- (3,5-bis (triisopropoxysilyl) propyl) phenylthiophen-2-yl) -2,5-bis (2-ethylhexyl) pyrrolo [3,4-c] pyrrole Synthesis of -1,4-dione>
3,6-bis (5-bromothiophen-2-yl) -2,5-bis (2-ethylhexyl) pyrrolo [3,4-c] pyrrole-1,4-dione (264 mg, 0.39 mmol), 1 , 3-bis (3- (triisopropoxysilyl) propyl) -5- (trimethylstannyl) benzene (710 mg, 0.97 mmol), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ , 17.7 mg, 0.020 mmol, Pd content: 10 mol%) and tri (2-furyl) phosphine (TFP, 19.5 mg, 0.077 mmol, 20 mol%) were mixed, and the resulting mixture was mixed under an argon atmosphere. Dehydrated tetrahydrofuran (30 ml) was added. The resulting solution was stirred at 70 ° C. for 3 hours, and the following reaction formula (XVI):

The reaction represented by Thereafter, the solvent was distilled off from the solution after the reaction under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 40/1) and preparative thin layer chromatography (developing solvent: chloroform) to give a dark blue solid (yield 207 mg, yield 46%). )

This dark blue solid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and 3,6-bis (5- (3,5-bis (triisopropoxysilyl) propyl) phenylthiophen-2-yl)- It was confirmed that it was 2,5-bis (2-ethylhexyl) pyrrolo [3,4-c] pyrrole-1,4-dione (DPP-4SiP). The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.64-0.68 (m, 8H), 0.87 (t, J = 7.2 Hz, 6H), 0.92 (t, J = 7.2 Hz) , 6H), 1.19 (d, J = 6.4 Hz, 72H), 1.24-1.42 (m, 16H), 1.72-1.80 (m, 8H), 1.91-2 .01 (m, 2H), 2.66 (t, J = 8.0 Hz, 8H), 4.08-4.11 (m, 4H), 4.21 (sept, J = 6.4 Hz, 12H) 7.00 (s, 2H), 7.29 (d, J = 1.2 Hz, 4H), 7.43 (d, J = 4.0 Hz, 2H), 8.96 (d, J = 4. 0Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 10.6, 11.8, 14.1, 23.1, 23.7, 25.1, 25.6, 28.6, 30.3, 39.2 39.2, 45.9, 64.8, 108.0, 123.8, 124.2, 128.4, 129.6, 132.9, 136.8, 139.9, 143.5, 150 .4, 161.7.
(Synthesis Example 3)
<[{2,5-bis (2-ethylhexyl) -2,3,5,6-tetrahydro-3,6-dioxopyrrolo [3,4-c] pyrrole-1,4-diyl}-{[2,2 Synthesis of '-(1,4-phenylene) bisthiophene] -5,5'-diyl}] alternating copolymer>
3,6-bis (5-bromothiophen-2-yl) -2,5-bis (2-ethylhexyl) pyrrolo [3,4-c] pyrrole-1,4-dione (250 mg, 0.37 mmol), 1 , 4-phenylenediboronic acid (60.7 mg, 0.37 mmol), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ , 16.7 mg, 18.5 μmol, Pd content: 10 mol%) , Triphenylphosphine (9.60 mg, 37.0 μmol, 10 mol%) and tripotassium phosphate (331.5 mg, 1.56 mmol) were mixed, and the resulting mixture was dehydrated toluene (10 ml) under an argon atmosphere. A 50 vol% aliquot of 336 in toluene (0.75 ml) and degassed distilled water (0.75 ml) were added. The resulting solution was stirred at 120 ° C. for 3 days, and the following reaction formula (XVII):

The reaction represented by Thereafter, the solution after the reaction was added dropwise to methanol to precipitate the polymerization component. The precipitate was collected by filtration, and the resulting residue was purified by Soxhlet extraction operation (methanol, hexane, chloroform). The fraction dissolved in chloroform was concentrated, and the resulting residue was washed again with methanol and dried under vacuum to obtain a dark black solid (yield 70 mg, 32%).

This dark black solid was identified by ¹ H-NMR measurement, and [{2,5-bis (2-ethylhexyl) -2,3,5,6-tetrahydro-3,6-dioxopyrrolo [3,4-c] pyrrole was identified. -1,4-diyl}-{[2,2 ′-(1,4-phenylene) bisthiophene] -5,5′-diyl}] alternating copolymer (pDPP-Ph). The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.89-1.38 (m, 28H), 1.93 (br, 2H), 4.08 (br, 4H), 7.26-7.78 ( m, 6H), 8.98 (br, 2H).

Example 1
DPP-2SiP obtained in Synthesis Example 1 was dissolved in tetrahydrofuran, and a 2 mol / L hydrochloric acid aqueous solution (5 μl) was added to the obtained solution (DPP-2SiP concentration: 0.33 mass%, 200 μl). Stir for minutes. The obtained sol solution was cast on a quartz substrate to produce a blue-violet cast film. The obtained cast film was heated under vacuum at 130 ° C. for 5 minutes to completely remove the remaining solvent, and a blue-violet organic silica thin film (DPP-2SiP, film thickness: 50 μm) was obtained.

  When the visible / ultraviolet (UV-vis) absorption spectrum of this organic silica thin film (DPP-2SiP) was measured, as shown by the solid line in FIG. 1, the organic silica thin film (DPP-2SiP) absorbed at a wavelength around 630 nm. It was confirmed that it has a maximum and can absorb visible light of 500 nm or more (having a wavelength at the absorption edge on the long wavelength side of 600 nm or more).

  Next, the organic silica thin film (DPP-2SiP) was heated in air at 130 ° C. for 48 hours. When the UV-vis absorption spectrum of the heated organic silica thin film (DPP-2SiP) was measured, as shown by the broken line in FIG. 1, the heated organic silica thin film (DPP-2SiP) also absorbed in the vicinity of a wavelength of 630 nm. It has a maximum and can absorb visible light of 500 nm or more (having a wavelength at the absorption edge on the long wavelength side of 600 nm or more). From the above results, it was confirmed that the organic silica thin film (DPP-2SiP) maintained its light absorption characteristics even after heating and was excellent in thermal stability.

(Example 2)
A blue-violet organic silica thin film (DPP-4SiP, film thickness: 30 μm) was obtained in the same manner as in Example 1 except that DPP-4SiP obtained in Synthesis Example 1 was used instead of DPP-2SiP. When the UV-vis absorption spectrum of this organic silica thin film (DPP-4SiP) was measured, as shown by the solid line in FIG. 2, the organic silica thin film (DPP-4SiP) had an absorption maximum in the vicinity of a wavelength of 630 nm, It was confirmed that the material can absorb visible light of 500 nm or more (having a wavelength at the absorption edge on the long wavelength side of 600 nm or more).

  Next, the organic silica thin film (DPP-4SiP) was heated in air at 130 ° C. for 48 hours. When the UV-vis absorption spectrum of the heated organic silica thin film (DPP-4SiP) was measured, as shown by the broken line in FIG. 2, the heated organic silica thin film (DPP-4SiP) also absorbed in the vicinity of a wavelength of 630 nm. It has a maximum and can absorb visible light of 500 nm or more (having a wavelength at the absorption edge on the long wavelength side of 600 nm or more). From the above results, it was confirmed that the organic silica thin film (DPP-4SiP) maintained its light absorption characteristics even after heating and was excellent in thermal stability.

(Comparative Example 1)
The pDPP-Ph obtained in Synthesis Example 3 was dissolved in chloroform, and the resulting solution (DPP-2SiP concentration: about 1% by mass, 100 μl) was cast on a quartz substrate. The obtained cast film was heated under vacuum at 130 ° C. for 5 minutes to completely remove the remaining solvent, and a blue polymer thin film (pDPP-Ph, film thickness: 120 μm) was obtained.

  When the UV-vis absorption spectrum of this polymer thin film (pDPP-Ph) was measured, as shown by the solid line in FIG. 3, the polymer thin film (pDPP-Ph) has an absorption maximum in the vicinity of a wavelength of 647 nm, It was confirmed that the material can absorb visible light of 500 nm or more (having a wavelength at the absorption edge on the long wavelength side of 600 nm or more).

  Next, the polymer thin film (pDPP-Ph) was heated in air at 130 ° C. for 48 hours. When the UV-vis absorption spectrum of the polymer thin film after heating (pDPP-Ph) was measured, as shown by the broken line in FIG. 3, the polymer thin film after heating (pDPP-Ph) had a visible light of 500 nm or more. A significant decrease in absorbance was observed in the region, and it was found that the light absorption characteristics before heating could not be maintained and the thermal stability was poor. Further, when the absorption spectrum shown in FIG. 3 was normalized by the absorbance at the maximum absorption maximum wavelength (647 nm), as shown in FIG. 4, in the polymer thin film after heating (pDPP-Ph), a short wavelength of 350 nm or less was obtained. Absorbance in the wavelength region increased. This means that decomposition products exist in the polymer thin film after heating (pDPP-Ph), and the polymer thin film (pDPP-Ph) is decomposed by heating in the atmosphere. I understood.

  As described above, according to the present invention, an organic silica material having a dithienyl diketopyrrolopyrrole skeleton exhibiting visible light absorption characteristics can be obtained. This organic silica material has high durability against oxygen and heat because the skeleton showing visible light absorption characteristics is cross-linked by a siloxane bond, and has excellent structural stability.

  Therefore, the organic silica-based material of the present invention is useful as an organic thin film solar cell material because it has visible light absorption characteristics and exhibits high durability against oxygen and heat. Specifically, when the organic silica material of the present invention is used as an organic p-type material for an organic thin-film solar cell, it is possible to extend the life of an element composed of the organic p-type material. In addition, due to excellent structural stability, it is also useful when the organic p-type material itself forms a structure in the device, such as a bulk heterojunction structure of an organic thin film solar cell.

Claims (4)

A repeating unit represented by the following formula (1):

[At least one group of R ^{1 to} R ³ and at least one group of R ^{4 to} R ^{6 in} the formula (1) are each independently a group represented by the following formula (2):

(In the formula (2), Z represents an arylene group having 6 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, an ethenylene group, an ethynylene group, an ether group, a carbonyl group, an amino group, an amide group, and an imide group. A group containing at least one selected from the group consisting of a single bond, R ^a represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group, k is 1 or 2, and i is An integer of 1 to 3, j is an integer of 0 to 2, 1 ≦ i + j ≦ 3, and a plurality of combinations of i and j are independent of each other in the group represented by the formula (2). And * is a binding site with an adjacent repeating unit.)
In the formula (1), the remaining groups of R ^{1 to} R ⁶ and R ^{7 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a phenoxy group, acetyl It is one selected from the group consisting of a group, a benzoyl group, an amino group, an amide group, an imide group, a nitro group, and a cyano group. ]
An organic silica-based material characterized by comprising:   2. The organosilica-based material according to claim 1, wherein Z in the formula (2) is a group including an arylene group having 6 to 20 carbon atoms that does not include an aromatic condensed ring.   The organosilica-based material according to claim 2, wherein Z in the formula (2) is a group in which a monocyclic aromatic ring and an alkylene group are bonded. The organic silica-based material according to any one of claims 1 to 3, wherein R ¹ and R ⁴ in the formula (1) are groups represented by the formula (2). .

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