Organic silane compound and mesoporous organic silica

Abstract

To provide mesoporous organic silica containing a phenanthroline ring, and an organic silane compound capable of obtaining the mesoporous organic silica.SOLUTION: For example, mesoporous organic silica is obtained using an organic silane compound containing a phenanthroline ring, which is a reaction product of the following formula.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an organosilane compound and mesoporous organosilica, and more particularly to an organosilane compound having a phenanthroline ring and mesoporous organosilica. [Background technology]

[0002] Conventionally, studies have been conducted to improve the properties of mesoporous silica by introducing organic groups having various functional groups into mesoporous silica in which mesopores are regularly arranged. For example, Japanese Patent Laid-Open Publication No. 2009-49346 (Patent Document 1) describes an energy conversion material comprising a porous body having an electron donor in its skeleton and an electron acceptor disposed in the pores of this porous body. The porous body having an electron donor in its skeleton is Cu(2,9-diphenyl-1,10-phenanthroline). 2+ Porous silica having organic groups that function as electron donors such as the above has been described.

[0003] Furthermore, Inorganic Chimica Acta, 2000, Vol. 297, pp. 156-161 (Non-Patent Document 1) and Microporous and Mesoporous Materials, 2008, Vol. 116, pp. 28-35 (Non-Patent Document 2) describe organosilane compounds in which a hydrolyzable silyl group and a phenanthroline ring are bonded via an alkylene linker containing a urea bond. ACS Appl. Mater. Interface, 2017, Vol. 9, pp. 3774-3784 (Non-Patent Document 3) describes organosilane compounds in which a hydrolyzable silyl group and a phenanthroline ring are bonded via an alkylene linker containing an amide bond. RSC Adv., 2023, Vol. 13, pp. 7828-7833 (Non-Patent Document 4) describes organosilane compounds in which a hydrolyzable silyl group and a phenanthroline ring are bonded via an alkylene linker consisting of a methylene group.

[0004] Furthermore, J.Phys.Chem.B, 2005, Vol. 109, pp. 15278-15287 (Non-Patent Document 5) describes mesoporous organic silica having a phenanthroline ring synthesized using the organic silane compound described in Non-Patent Document 1 and a tetraalkoxysilane, and J.Phys.Chem.C, 2009, Vol. 113, pp. 2603-2610 (Non-Patent Document 6) describes mesoporous organic silica having a phenanthroline ring synthesized using the organic silane compound described in Non-Patent Document 2 and an ethane-bridged organic silane compound. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-49346 [Non-patent literature]

[0006] [Non-Patent Document 1] Kloster et al., Inorganica Chimica Acta, 2000, 297, 156-161 [Non-patent document 2] Guo et al., Microporous and Mesoporous Materials, 2008, Vol. 116, pp. 28-35 [Non-patent document 3] Yuan et al., ACS Appl. Mater. Interface, 2017, Vol. 9, pp. 3774-3784 [Non-patent document 4] Lin et al., RSC Adv. 2023, vol. 13, pp. 7828–7833 [Non-Patent Document 5] Peng et al., J.Phys.Chem.B 2005, Vol. 109, pp. 15278-15287 [Non-patent document 6] Guo et al., J.Phys.Chem.C 2009, Vol. 113, pp. 2603-2610 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the organosilane compounds described in Non-Patent Documents 1 to 4 have alkylene groups in the linker moiety that are prone to conformational changes, which causes the problem that the structure around the phenanthroline ring in the mesoporous organosilicas synthesized from these organosilane compounds becomes flexible.Furthermore, the mesoporous organosilicas described in Non-Patent Documents 5 and 6 do not necessarily have sufficient bond stability under hydrolysis or heating conditions, resulting in the loss of the phenanthroline ring.

[0008] The present invention has been made in view of the problems associated with the above-mentioned conventional techniques, and aims to provide mesoporous organic silica having a strong structure around the phenanthroline ring, as well as an organic silane compound from which this mesoporous organic silica can be obtained.

[0009] These problems (issues) do not preclude the existence of other problems. Furthermore, each aspect of the present invention described below does not necessarily solve all of these problems (issues). Furthermore, other problems (issues) may be identified from the description of the specification, drawings, or claims. [Means for solving the problem]

[0010] As a result of intensive research into the above-mentioned problems, the inventors of the present invention discovered that it is possible to obtain mesoporous organic silica having a strong structure around the phenanthroline ring and excellent bonding stability, thereby completing the present invention.

[0011] The first aspect of the present invention for solving the above problem is:

[0012] [ka] [In formula (1), R is the following formula (2):

[0013] [ka] In formula (2), R 1 ~R 5 At least one group of the formula (3):

[0014] [ka]

[0015] (R a represents an alkyl group having 1 to 6 carbon atoms, and R 1 ~R 5 and the remaining groups are each independently a hydrogen atom, a halogen atom, or a monovalent or divalent organic group selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, a phenoxy group, a hydroxy group, an acetyl group, a benzoyl group, an amino group, an amido group, an imido group, a nitro group, and a cyano group.

[0016] According to the first aspect, it is possible to provide an organosilane compound that can provide mesoporous organosilica having a strong structure around the phenanthroline ring and excellent bonding stability.

[0017] In a second aspect of the present invention, in formula (1), R is represented by the following formula (4) or the following formula (5):

[0018] [ka]

[0019] [ka]

[0020] (In formula (4) and formula (5), R a represents an alkyl group having 1 to 6 carbon atoms).

[0021] According to the second aspect, it is possible to provide an organosilane compound that can give mesoporous organosilica having a stronger structure around the phenanthroline ring and excellent bonding stability.

[0022] A third aspect of the present invention is a compound represented by the formula R a is an isopropyl group.

[0023] According to the third aspect, an organosilane compound can be provided that can produce mesoporous organosilica having a stronger structure around the phenanthroline ring and excellent bonding stability. Furthermore, the organosilane compound of this aspect is easily handled because it is moderately hydrolyzed.

[0024] A fourth aspect of the present invention is a mesoporous organosilica characterized by being a polymer of an organosilane compound according to any one of the first to third aspects.

[0025] According to the fourth aspect, it is possible to provide a mesoporous organic silica having a strong structure around the phenanthroline ring and excellent bonding stability.

[0026] A fifth aspect of the present invention is a compound represented by the following formula (6):

[0027] [ka] [wherein R is the following formula (7):

[0028] [ka]

[0029] (X in formula (7) represents an arylene group, R beach independently represents a hydrogen atom or a silyl group, i is an integer of 1 to 3, j is an integer of 0 to 2, i+j=3 is satisfied, and k is an integer of 1 to 5).

[0030] According to the fifth aspect, it is possible to provide a mesoporous organic silica having a stronger structure around the phenanthroline ring and excellent bonding stability.

[0031] A sixth aspect of the present invention is a mesoporous organosilica characterized by being a copolymer of the organosilane compound according to any one of the first to third aspects and a compound represented by the following formula (8):

[0032] [ka]

[0033] (In formula (8), Y represents a divalent to tetravalent organic group, and R d each independently represents an alkyl group having 1 to 6 carbon atoms, and each n independently represents an integer of 1 or 2.

[0034] According to the sixth aspect, it is possible to provide mesoporous organic silica in which the phenanthroline ring content in the mesoporous organic silica can be adjusted as desired, and in which the structure around the phenanthroline ring is strong and has excellent bonding stability.

[0035] A seventh aspect of the present invention is a compound represented by the following formula (6):

[0036] [ka] [wherein R is the following formula (7):

[0037] [ka]

[0038] (In formula (7), X represents an arylene group, and R b each independently represents a hydrogen atom or a silyl group, i is an integer of 1 to 3, j is an integer of 0 to 2, i+j=3 is satisfied, and k is an integer of 1 to 5). and a group represented by the following formula (9):

[0039] [ka]

[0040] (In formula (9), Y represents a divalent to tetravalent organic group, and R c each independently represents a hydrogen atom or a silyl group; each l independently represents an integer of 1 to 3; each m independently represents an integer of 1 to 3; and each n independently represents an integer of 1 to 2.

[0041] According to the seventh aspect, the phenanthroline ring content in the mesoporous organic silica can be adjusted as desired, and the structure around the phenanthroline ring is even stronger, making it possible to provide mesoporous organic silica with excellent bonding stability. [Brief explanation of the drawings]

[0042] [Figure 1] FIG. 1 is a chemical reaction formula showing an example of the synthesis of an organosilane compound according to the present invention. [Figure 2] 2(a) and 2(b) are chemical formulas showing examples of structures contained in the mesoporous organic silica of the present invention. [Figure 3] FIG. 3 is a chemical formula showing a specific example of a portion capable of forming a siloxane bond (Si—O—Si) in the crosslinking group of an organosilane compound. [Figure 4] FIG. 4 is a chemical reaction formula showing an example of the synthesis of the organosilane compound of Example 1. [Figure 5]FIG. 5 is a diagram showing the results of 1H-NMR measurement of 3,8-bis(4-(triisopropoxysilyl)phenyl)-1,10-phenanthroline obtained in Example 1. [Figure 6] FIG. 6 is a graph showing the nitrogen adsorption / desorption isotherm of the bis(silylphenylene) Phen-PMO obtained in Example 1. [Figure 7] FIG. 7 is a transmission electron microscope image of the bis(silylphenylene) Phen-PMO obtained in Example 1. [Figure 8] FIG. 8 is a graph showing the nitrogen adsorption / desorption isotherm of the bis(silylphenylene) Phen-(C2H4)-PMO obtained in Example 1. [Figure 9] FIG. 9 is a chemical reaction formula showing the first chemical reaction of Example 2. [Figure 10] FIG. 10 is a chemical reaction formula showing the second chemical reaction of Example 2. [Figure 11] FIG. 11 is a diagram showing the results of 1H-NMR measurement of 3,8-bis(3,5-bis(triisopropoxysilyl)phenyl)-1,10-phenanthroline obtained in Example 2. [Figure 12] FIG. 12 is a transmission electron microscope image of bis(disilylphenylene) Phen-PMO obtained by Synthesis 1 in Example 2. [Figure 13] FIG. 13 is a graph showing the nitrogen adsorption / desorption isotherm of bis(disilylphenylene) Phen-PMO obtained by Synthesis 1 in Example 2. [Figure 14] FIG. 14 is a graph showing the nitrogen adsorption / desorption isotherm of bis(disilylphenylene) Phen-PMO obtained by Synthesis 2 in Example 2. [Figure 15] FIG. 15 is a graph showing the nitrogen adsorption / desorption isotherm of bis(disilylphenylene) Phen-(C 2 H 4 )-PMO obtained in Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0043] Hereinafter, embodiments of the organosilane compound according to the present invention will be described with reference to the accompanying drawings, but the present invention is not limited to the following embodiments.

[0044] (Embodiment 1) <Organosilane compounds> First, the organosilane compound of the present invention will be described. The organosilane compound of the present invention is a compound represented by the following formula (1):

[0045] [ka] [In formula (1), R is the following formula (2):

[0046] [ka]

[0047] (In formula (2), R 1 ~R 5 At least one group of the formula (3):

[0048] [ka]

[0049] (R a represents an alkyl group having 1 to 6 carbon atoms. is a group represented by R 1 ~R 5 and the remaining groups are each independently a hydrogen atom, a halogen atom, or a monovalent or divalent organic group selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, a phenoxy group, a hydroxy group, an acetyl group, a benzoyl group, an amino group, an amido group, an imido group, a nitro group, and a cyano group.

[0050] In addition, R arepresents an alkyl group having 1 to 6 carbon atoms, and is preferably a methyl group, an ethyl group, an n-butyl group, or an isopropyl group from the viewpoint of ease of preparation of mesoporous organic silica described below and ease of handling of the organic silane compound.

[0051] In the organosilane compound of the present invention, the group represented by formula (3) is a crosslinking group, and the phenanthroline ring containing the arylene group is three-dimensionally crosslinked by the siloxane bond (Si-O-Si bond) in the crosslinking group (crosslinking group) formed by the reaction of this crosslinking group, thereby obtaining a mesoporous organosilica that exhibits high durability against mechanical and chemical action. Note that the groups represented by formula (3) may be the same or different.

[0052] Since the arylene group has a strong aromatic planar structure, it has excellent durability against mechanical and chemical action. By using such an organosilane compound, it is possible to obtain mesoporous organic silica having a periodic mesoporous structure, a strong structure around the phenanthroline ring, and excellent bonding stability.

[0053] Here, R in formula (1) is the following formula (4) or the following formula (5):

[0054] [ka]

[0055] [ka]

[0056] (In formula (4) and formula (5), R a represents an alkyl group having 1 to 6 carbon atoms) By using such an organosilane compound, it is possible to obtain mesoporous organosilica having a periodic mesoporous structure, a stronger structure around the phenanthroline ring, and excellent bonding stability.

[0057] In addition, R a represents an alkyl group having 1 to 6 carbon atoms, and is preferably a methyl group, an ethyl group, an n-butyl group, or an isopropyl group from the viewpoint of ease of preparation of mesoporous organic silica described below and ease of handling of the organic silane compound.

[0058] The organosilane compounds of the present invention can be produced, for example, by the chemical reaction scheme shown in Figure 1. In this chemical reaction scheme, the structure of an organometallic reagent, for example, an organozinc reagent, is appropriately changed depending on the structure of the target organosilane compound, and cross-coupling, for example, Negishi cross-coupling, is carried out to produce the target organosilane compounds (organosilane compounds represented by formulas (1) to (3)).

[0059] <Mesoporous organic silica> Next, the mesoporous organosilica of the present invention will be described. The mesoporous organosilica of the present invention is a polymer of the organosilane compound of the present invention described above.

[0060] The mesoporous organic silica of the present invention is, for example, a compound represented by the following formula (6):

[0061] [ka] wherein R in formula (6) is represented by the following formula (7):

[0062] [ka] The mesoporous organic silica includes polymers of the organic silane compounds of the present invention represented by formulas (1) to (3).

[0063] In the structure of the mesoporous organic silica of the present invention, phenanthroline rings containing arylene groups are three-dimensionally crosslinked by siloxane bonds (Si-O-Si bonds) in the crosslinking groups, as shown in Figure 2. Figure 3 shows specific examples of moieties that can be siloxane-bonded.

[0064] Therefore, depending on the position (location) of the siloxane bond in the crosslinking group, the mesoporous organic silica of the present invention has a three-dimensionally complex structure, similar to conventional mesoporous organic silica (e.g., the mesoporous organic silica described in Japanese Patent No. 7436985).

[0065] X in formula (7) represents an arylene group, and R b each independently represents a hydrogen atom or a silyl group, and examples of the silyl group include alkylsilyl groups such as trimethylsilyl. In formula (7), i is an integer of 1 to 3 (preferably an integer of 2 to 3), j in formula (7) is an integer of 0 to 2 (preferably an integer of 0 to 1), and i+j=3. k is an integer of 1 to 5 (preferably an integer of 1 or 2).

[0066] Furthermore, when the proportion of the groups represented by formula (6) and formula (7) is less than 100 mol%, the groups other than the groups represented by formula (6) and formula (7) (hereinafter referred to as "other groups") are preferably, for example, groups represented by the following formula (9).

[0067] [ka] Y in formula (9) is a divalent to tetravalent organic group, and examples thereof include an alkylene group (preferably having 1 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms) and an arylene group (preferably having 6 to 12 carbon atoms). c each independently represents a hydrogen atom or a silyl group, and examples of the silyl group include an alkylsilyl group such as a trimethylsilyl group. In formula (9), each 1 independently represents an integer of 1 to 3 (preferably an integer of 2 to 3), each m independently represents an integer of 1 to 3 (preferably an integer of 2 to 3), and each n independently represents an integer of 1 or 2.

[0068] The mesoporous organic silica containing groups represented by formula (6), formula (7), and formula (9) can be synthesized by polymerizing the organic silane compounds represented by the above formulas (1) to (3) with the organic silane compound represented by the following formula (8) in any ratio.

[0069] [ka] In formula (8), Y represents a divalent to tetravalent organic group, and R d each independently represents an alkyl group having 1 to 6 carbon atoms, and each n independently represents an integer of 1 or 2.

[0070] Here, the mesoporous organic silica of the present invention has a structure with mesopores (mesoporose structure). The average pore diameter (central pore diameter) in such a mesopore structure is preferably 1 nm to 50 nm, more preferably 1.5 nm to 30 nm. If the central pore diameter is less than 1 nm, the effect on substance diffusion is significant, making it difficult for metal ions to coordinate. Furthermore, even if metal ions are immobilized and applied to a heterogeneous immobilized catalyst, catalytic reactions tend to be difficult to occur. On the other hand, if the central pore diameter exceeds 50 nm, it tends to be difficult to form a periodic mesoporous structure.

[0071] The total pore volume in the mesopore structure is 0.1 to 2 cm 3 / g is preferred, and 0.2 to 1 cm 3 / g is more preferable. 3 If the metal ion content is less than 1 / g, even if the metal ions are immobilized and applied to a heterogeneous immobilized catalyst, the amount of immobilized metal ions per unit weight of the heterogeneous immobilized catalyst is limited, and therefore, the catalytic reaction tends to be difficult to occur.

[0072] Furthermore, in the mesoporous organic silica of the present invention, the specific surface area is 100 to 1500 m 2 / g is preferred, and 250 to 1000m 2 / g is more preferable.2 If the metal ion content is less than 1 / g, even if the metal ions are immobilized and applied to a heterogeneous immobilized catalyst, the amount of immobilized metal ions per unit weight of the heterogeneous immobilized catalyst is limited, and therefore, the catalytic reaction tends to be difficult to occur.

[0073] The central pore diameter can be determined by the Barrett-Joyner-Halenda (BJH) method or the Density-Functional-Theory (DFT) method based on the nitrogen adsorption / desorption isotherm, the total pore volume can be determined by the t-plot method based on the nitrogen adsorption / desorption isotherm, and the specific surface area can be determined by the Brunauer-Emmett-Teller (BET) method based on the nitrogen adsorption / desorption isotherm.

[0074] Furthermore, the X-ray diffraction pattern of the mesoporous organic silica of the present invention preferably has one or more diffraction peaks at diffraction angles corresponding to d values ​​of 1.5 to 30 nm. An X-ray diffraction peak indicates the presence of a periodic structure with a d value corresponding to that peak angle in the sample. Therefore, the presence of one or more diffraction peaks at diffraction angles corresponding to d values ​​of 1.5 to 30 nm indicates the presence of a regular mesopore structure in which pores are regularly arranged at intervals of 1.5 to 30 nm. Mesoporous organic silica with such a regular mesopore structure has a large specific surface area and pore volume, which is advantageous for the adsorption of metal ions and, when metal ions are immobilized and used as a solid catalyst, is advantageous for catalytic reactions within the pores.

[0075] The mesoporous organosilica of the present invention can be produced, for example, by hydrolyzing and polycondensing the organosilane compounds represented by the above formulas (1) to (3) in the presence of a surfactant by a known method to form an organosilica mesostructure containing the surfactant, and then removing the surfactant from the organosilica mesostructure by a known method. In this reaction, the hydrolyzable silyl groups of the organosilane compounds represented by formulas (1) to (3) are hydrolyzed to produce silanol groups (Si-OH), which are then polycondensed to form siloxane bonds (Si-O-Si). This allows the production of mesoporous organosilica having structures such as those shown in Figures 2(a) and 2(b). In Figures 2(a) and 2(b), X represents an arylene group, and R represents an arylene group. b each independently represents a hydrogen atom or a silyl group.

[0076] Furthermore, when producing the mesoporous organic silica of the present invention, the proportion of the organic silane compounds represented by formulas (1) to (3) is not particularly limited as long as it is 1 mol% or more relative to 100 mol% of all organic silane compounds (including other organic silane compounds). However, when metal ions are immobilized on the resulting mesoporous organic silica and applied to a heterogeneous immobilized catalyst, from the viewpoint of achieving both stabilization of the periodic mesoporous structure and ensuring an appropriate amount of immobilized metal ions per unit weight of the heterogeneous immobilized catalyst, the proportion of the organic silane compounds represented by formulas (1) to (3) is preferably 1 mol% to 90 mol%, more preferably 2 mol% to 80 mol%, and particularly preferably 5 mol% to 50 mol%.

[0077] When producing the mesoporous organic silica of the present invention, if the proportion of the organic silane compounds represented by formulas (1) to (3) is less than 100 mol%, substances other than the organic silane compounds represented by formulas (1) to (3) include, for example, the organic silane compound represented by formula (8) described above, and preferably 1,2-bis(triethoxysilyl)ethane (BTEE).

[0078] When producing the mesoporous organic silica of the present invention, the proportion of the organic silane compound represented by the above formula (8) is not particularly limited as long as it is 99 mol% or less relative to 100 mol% of all organic silane compounds. However, when metal ions are immobilized on the resulting mesoporous organic silica and applied to a solid catalyst, from the viewpoint of achieving both stabilization of the periodic mesoporous structure and ensuring an appropriate amount of immobilized metal ions, the proportion is preferably 99 to 10 mol%, more preferably 98 to 20 mol%, and particularly preferably 95 to 50 mol%.

[0079] The method of hydrolysis and (poly)condensation used to produce the mesoporous organic silica of the present invention is not particularly limited, and can be, for example, the method described in JP 2014-193457 A or JP 2017-029926 A. Furthermore, examples of surfactants used to produce the mesoporous organic silica of the present invention include those described in JP 2014-193457 A or JP 2017-029926 A. By using such surfactants, mesoporous organic silica having regular mesopores can be obtained. Furthermore, examples of methods for removing such surfactants from the organic silica mesostructure include the methods described in JP 2014-193457 A or JP 2017-029926 A.

[0080] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Furthermore, organosilane compounds and mesoporous organosilicas that are included in the present invention but are not described in the following examples can also be prepared in the same manner by those skilled in the art, with reference to the following examples.

[0081] Example 1 <Synthesis of 3,8-bis(4-(triisopropoxysilyl)phenyl)-1,10-phenanthroline> 3,8-bis(4-(triisopropoxysilyl)phenyl)-1,10-phenanthroline, an organosilane compound represented by the following formula (10), was prepared as follows.

[0082] [ka] First, as shown in Figure 4, 280 mg of (4-bromophenyl)triisopropoxysilane and 50 mg of magnesium powder were reacted in 2 mL of tetrahydrofuran at 60 °C to prepare the corresponding Grignard reagent. Next, 103 mg of zinc chloride was reacted with this Grignard reagent to prepare a solution containing an organozinc reagent. Subsequently, 119 mg of 3,8-dibromo-1,10-phenanthroline and 20 mg of tetrakis(triphenylphosphine)palladium were added to the solution containing the organozinc reagent at -90 °C. The solution was gradually returned to room temperature and reacted for 13 hours. The product was then purified by column chromatography using amino-modified silica gel to obtain a colorless powder (yield: 50%).

[0083] This powder 1 The powder was identified by H-NMR measurement and was found to be 3,8-bis(4-(triisopropoxysilyl)phenyl)-1,10-phenanthroline. The results are shown in Figure 5. 1 H NMR(600MHz,CDCl3):9.47(d,J=2.3Hz,2H),8.43(d,J=2.3Hz,2H),7.91(s,2H),7.89-7.86(m,4H),7.81-7.79(m,4H),4.33(sept,J=6.1Hz,6H),1.26 ppm(d,J=6.1Hz,36H)

[0084] <Synthesis of mesoporous organosilica (bis(silylphenylene) Phen-PMO) polymerized solely from 3,8-bis(4-(triisopropoxysilyl)phenyl)-1,10-phenanthroline> First, 22.2 mL of distilled water, 2.46 g (7.08 mmol) of trimethylstearyl ammonium chloride (C18TMACl), and 0.13 g of 6N sodium hydroxide were placed in a 200 mL flask. The flask was then placed in a water bath at 50°C and stirred vigorously. Using a syringe pump, a first mixture containing 328 mg of 3,8-bis(4-(triisopropoxysilyl)phenyl)-1,10-phenanthroline and 2 mL of ethanol was added to the flask. Specifically, the first mixture was added dropwise at a flow rate of 1.0 mL / h for 10 minutes, followed by stirring for 10 minutes. This procedure was repeated three times. The remaining first mixture was then added dropwise at a flow rate of 1.0 mL / h. The mixture was then subjected to ultrasonic treatment (40 kHz) for 2 hours while stirring at 50°C.

[0085] The flask was then placed in a 50°C oil bath and stirred for 24 hours. The precipitate was then collected by pressure filtration. 200 mL of water was added to the precipitate, and the mixture was allowed to stand at 95°C for 24 hours. The mixture was then pressure filtered, and the resulting precipitate was added to a second mixture of 72.3 mL of ethanol and 2.0 mL of 2N hydrochloric acid, followed by stirring at room temperature (e.g., 20°C to 25°C) for 12 hours. The second mixture was then pressure filtered to obtain a powder of mesoporous organic silica (bis(silylphenylene)Phen-PMO).

[0086] The nitrogen adsorption / desorption isotherm of the obtained bis(silylphenylene)Phen-PMO was measured using a specific surface area / pore size distribution analyzer (Microtrack-Bell "BELSORP MAX") and the results are shown in Figure 6 (in the figure, black circles indicate adsorption and white circles indicate desorption). As can be seen from this figure, this nitrogen adsorption / desorption isotherm is classified as type 4 of the IUPAC classification of adsorption / desorption isotherms, indicating that bis(silylphenylene)Phen-PMO has mesopores. Furthermore, based on the obtained nitrogen adsorption / desorption isotherm, the specific surface area of ​​bis(silylphenylene)Phen-PMO was calculated by the Brunauer-Emmett-Teller (BET) method (calculated in the range of P / P = 0.1 to 0.2) to be 1146 m 2 / g.

[0087] Synthesis of mesoporous organosilica (bis(silylphenylene)Phen-(C2H4)-PMO) by copolymerization of 3,8-bis(4-(triisopropoxysilyl)phenyl)-1,10-phenanthroline and BTEE First, 0.811 g of a surfactant (trade name: Pluronic P123 (Sigma-Aldrich)), 1.29 g of potassium chloride, 7.1 mL of distilled water, and 1 mL of concentrated hydrochloric acid were placed in a 110 mL vial and sealed. The mixture was stirred for 1 hour while ice-cooling, then heated to 45°C and stirred for 30 minutes. Next, 1.4 mL of an ethanol solution (45°C) containing 115 mg (0.156 mmol) of 3,8-bis(4-(triisopropoxysilyl)phenyl)-1,10-phenanthroline and 312 mg (0.88 mmol) of BTEE was added to the mixture in one go. The vial was then sealed with a screw cap and stirred at 45°C for 24 hours.

[0088] The screw cap was then opened, the stir bar removed from the vial, and the screw cap was replaced to seal the vial. The vial was then heated to 100°C and allowed to stand for 24 hours. After cooling to room temperature (e.g., 20°C to 25°C), the mixture was filtered under pressure to obtain a pale yellow precipitate.

[0089] The pale yellow precipitate was washed with 10 mL of distilled water and dried under vacuum at 60 °C. Then, 0.7 mL of 2 M hydrochloric acid and 25 mL of ethanol were added to the pale yellow precipitate, and the mixture was stirred at room temperature (e.g., 20 °C to 25 °C) for 16 hours. The pale yellow precipitate was then collected by pressure filtration. The pale yellow precipitate was then washed with 10 mL of distilled water and 10 mL of ethanol and dried under vacuum at 60 °C to obtain mesoporous organosilica (bis(silylphenylene)Phen-(C2H4)-PMO). A transmission electron microscope image of the resulting bis(silylphenylene)Phen-(C2H4)-PMO is shown in Figure 7.

[0090] The nitrogen adsorption / desorption isotherm of the obtained bis(silylphenylene) Phen-(C2H4)-PMO was measured using a specific surface area / pore size distribution analyzer (Microtrac-Bell "BELSORP MAX") and the results are shown in Figure 8 (in the figure, black circles indicate adsorption and white circles indicate desorption). As can be seen from this figure, this nitrogen adsorption / desorption isotherm is classified into Type 4 of the IUPAC classification of adsorption / desorption isotherms, indicating that bis(silylphenylene) Phen-(C2H4)-PMO has mesopores. Furthermore, based on the obtained nitrogen adsorption / desorption isotherm, the specific surface area of ​​bis(silylphenylene) Phen-(C2H4)-PMO was calculated by the BET method (calculated in the range of P / P0 = 0.1 to 0.2) to be 758 m 2 The central pore diameter of bis(silylphenylene) Phen-(C2H4)-PMO was calculated by the BJH (Barrett-Joyner-Halenda) method and found to be 7.2 nm.

[0091] Example 2 <Synthesis of 3,8-bis(3,5-bis(triisopropoxysilyl)phenyl)-1,10-phenanthroline> 3,8-bis(3,5-bis(triisopropoxysilyl)phenyl)-1,10-phenanthroline, an organosilane compound represented by the following formula (11), was produced as follows.

[0092] [ka] First, 2.51 g of 1,3,5-tribromobenzene and 6.58 g of triisopropoxysilane were stirred in 10 mL of dimethylformamide in the presence of 30 mg of [Rh(MeCN)2(COD)](BF4), 6 g of tetrabutylammonium iodide, and 6 mL of triethylamine while heating to 100°C for 24 hours to carry out the first chemical reaction shown in Figure 9. The reaction solution was then purified by silica gel column chromatography to obtain (5-bromo-1,3-phenylene)bis(triisopropoxysilane) in a 57% yield. Next, as shown in Figure 10, 2.58 g of (5-bromo-1,3-phenylene)bis(triisopropoxysilane) was reacted with 328 mg of magnesium powder in 20 mL of tetrahydrofuran under reflux conditions in the presence of 3 drops of 1,2-dibromoethane to prepare the corresponding Grignard reagent. This Grignard reagent was then reacted with 620 mg of zinc chloride to prepare a solution containing an organozinc reagent. This solution containing the organozinc reagent was then added to a solution of 770 mg of 3,8-dibromo-1,10-phenanthroline and 262 mg of tetrakis(triphenylphosphine)palladium in 30 mL of tetrahydrofuran at room temperature and allowed to react for 16 hours. The reaction solution was purified by recycle preparative gel permeation chromatography to obtain a yellow oil (yield: 50%).

[0093] This oil 1 The oil was identified by H-NMR measurement and was found to be 3,8-bis(3,5-bis(triisopropoxysilyl)phenyl)-1,10-phenanthroline. The results are shown in Figure 11.

[0094] 1 H NMR(600MHz, CDCl3):9.47(d,J=2.3Hz,2H),8.42(d,J=2.3Hz,2H),8.15(d,J=1 .0Hz,4H),8.11(t,J=1.0Hz,2H),7.92(s,2H),4.33(sept,J=6.1Hz,12H),1.26 ppm(d,J=6.1Hz,72H)

[0095] <Synthesis of mesoporous organosilica (bis(disilylphenylene) Phen-PMO) polymerized solely from 3,8-bis(3,5-bis(triisopropoxysilyl)phenyl)-1,10-phenanthroline 1> First, 22.2 mL of distilled water, 0.42 g (1.18 mmol) of trimethylstearyl ammonium chloride (C18TMACl), and 0.26 mL of 6N sodium hydroxide were placed in a 200 mL flask. The flask was then placed in a 50°C water bath with vigorous stirring. Using a syringe pump, a third mixture containing 554 mg (0.50 mmol) of 3,8-bis(3,5-bis(triisopropoxysilyl)phenyl)-1,10-phenanthroline and 1.25 mL of ethanol was added to the flask. Specifically, the third mixture was added dropwise at a flow rate of 1.0 mL / h for 10 minutes, followed by stirring for 10 minutes. This procedure was repeated three times. The remaining third mixture was then added dropwise at a flow rate of 1.0 mL / h. The mixture was then subjected to ultrasonic treatment (40 kHz) for 2 hours while stirring at 50°C.

[0096] The flask was then placed in an oil bath at 50°C or 95°C and stirred for 24 hours. The mixture was then pressure-filtered to recover the precipitate. 200 mL of water was added to the precipitate and allowed to stand at 95°C for 24 hours. The resulting precipitate was then pressure-filtered, and added to a fourth mixture of 72.3 mL of ethanol and 2.0 mL of 2N hydrochloric acid, followed by stirring at room temperature (e.g., 20°C to 25°C) for 12 hours. The fourth mixture was then pressure-filtered to obtain a powder of mesoporous organic silica (bis(disilylphenylene)Phen-PMO). A transmission electron microscope image of the resulting bis(disilylphenylene)Phen-PMO is shown in Figure 12.

[0097] The nitrogen adsorption / desorption isotherm of the resulting bis(disilylphenylene)Phen-PMO was measured using a specific surface area / pore size distribution analyzer (Microtrack-Bell "BELSORP MAX") and the results are shown in Figure 13 (in the figure, black circles indicate adsorption and white circles indicate desorption). As can be seen from this figure, the nitrogen adsorption / desorption isotherm falls into type 4 of the IUPAC classification of adsorption / desorption isotherms, indicating that bis(disilylphenylene)Phen-PMO has mesopores.

[0098] <Synthesis of mesoporous organosilica (bis(disilylphenylene)Phen-PMO) polymerized solely from 3,8-bis(3,5-bis(triisopropoxysilyl)phenyl)-1,10-phenanthroline 2> First, 996 mg of a surfactant (trade name: BrijS10 (Sigma-Aldrich)), 3.0 g of sodium chloride, 26.1 mL of distilled water, and 1.73 mL of concentrated hydrochloric acid were placed in a 110 mL vial, heated to 60°C, and stirred for 2 hours. Next, 0.2 mL of an ethanol solution (60°C) containing 448 mg (0.39 mmol) of 3,8-bis(3,5-bis(triisopropoxysilyl)phenyl)-1,10-phenanthroline was added dropwise to the mixture, and then stirred at 60°C for 24 hours.

[0099] Thereafter, the stir bar was removed from the vial, and the mixture was allowed to stand for 24 hours while being heated to 80° C. After that, the mixture was cooled to room temperature (for example, 20° C. to 25° C.), and then pressure filtered to obtain a precipitate.

[0100] The precipitate was washed with 30 mL of distilled water and dried under vacuum at 50°C. Then, 1.4 mL of 2 M hydrochloric acid and 50 mL of ethanol were added to the precipitate, and the mixture was stirred at room temperature (e.g., 20°C to 25°C) for 16 hours. The precipitate was then collected by pressure filtration. The precipitate was then washed with distilled water and ethanol, and dried under vacuum at 50°C to obtain mesoporous organic silica (bis(disilylphenylene)Phen-PMO).

[0101] The nitrogen adsorption / desorption isotherm of the obtained bis(disilylphenylene)Phen-PMO was measured using a specific surface area / pore size distribution analyzer (Microtrack-Bell "BELSORP MAX") and the results are shown in Figure 14 (in the figure, black circles indicate adsorption and white circles indicate desorption). As can be seen from this figure, this nitrogen adsorption / desorption isotherm falls into Type 4 of the IUPAC classification of adsorption / desorption isotherms, indicating that bis(disilylphenylene)Phen-PMO has mesopores. Furthermore, based on the obtained nitrogen adsorption / desorption isotherm, the specific surface area of ​​bis(disilylphenylene)Phen-PMO was calculated by the BET method (calculated in the range of P / P = 0.1 to 0.2) to be 863 m 2 / g.

[0102] Synthesis of mesoporous organosilica (bis(disilylphenylene)Phen-(C2H4)-PMO) by copolymerization of 3,8-bis(3,5-bis(triisopropoxysilyl)phenyl)-1,10-phenanthroline and BTEE First, 0.406 g of a surfactant (trade name: Pluronic P123 (Sigma-Aldrich)), 2.59 g of potassium chloride, 14.3 mL of distilled water, and 2.03 mL of concentrated hydrochloric acid were placed in a 110 mL vial, and the mixture was stirred for 1 hour while ice-cooling, then heated to 45°C and stirred for 30 minutes. Next, 0.5 mL of an ethanol solution (45°C) containing 358 mg (0.031 mmol) of 3,8-bis(3,5-bis(triisopropoxysilyl)phenyl)-1,10-phenanthroline and 625 mg (1.76 mmol) of BTEE was added to the mixture all at once, and the mixture was stirred at 45°C for 24 hours.

[0103] The stir bar was then removed from the vial, and the mixture was left standing for 24 hours while being heated to 100°C. After cooling to room temperature (e.g., 20°C to 25°C), the mixture was filtered under pressure to obtain a precipitate.

[0104] The precipitate was washed with 30 mL of distilled water and dried under vacuum at 50°C. 2.8 mL of 2 M hydrochloric acid and 100 mL of ethanol were then added to the precipitate, and the mixture was stirred at room temperature (e.g., 20°C to 25°C) for 16 hours. The precipitate was then collected by pressure filtration. The precipitate was then washed with distilled water and ethanol, and dried under vacuum at 50°C to obtain mesoporous organosilica (bis(disilylphenylene)Phen-(C2H4)-PMO).

[0105] The nitrogen adsorption / desorption isotherm of the resulting bis(disilylphenylene)Phen-(C2H4)-PMO was measured using a specific surface area / pore size distribution analyzer (Microtrack-Bell "BELSORP MAX") and the results are shown in Figure 15 (in the figure, black circles indicate adsorption and white circles indicate desorption). As can be seen from this figure, the nitrogen adsorption / desorption isotherm falls into type 4 of the IUPAC classification of adsorption / desorption isotherms, indicating that bis(disilylphenylene)Phen-(C2H4)-PMO has mesopores.

Claims

1. The following formula (1): [In the formula (1), R is the following formula (2): (In the formula (2), R １ ~R ５ At least one group of the following formula (3): (R ａ represents an alkyl group having 1 to 6 carbon atoms) is a group represented by R １ ~R ５ the remaining groups are each independently a hydrogen atom, a halogen atom, or a monovalent or divalent organic group selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, a phenoxy group, a hydroxy group, an acetyl group, a benzoyl group, an amino group, an amido group, an imido group, a nitro group, and a cyano group. An organosilane compound represented by the formula:

2. In the formula (1), R is represented by the following formula (4) or (5): 【change】 【Transformation 5】 (In the formula (4) and the formula (5), R ａ represents an alkyl group having 1 to 6 carbon atoms) The organosilane compound according to claim 1, characterized in that the organic silane compound is a group represented by the formula:

3. R ａ 3. The organosilane compound according to claim 2, wherein is an isopropyl group.

4. A mesoporous organic silica, which is a polymer of the organic silane compound according to any one of claims 1 to 3.

5. The following formula (6): [In the formula (6), R is the following formula (7): (X in the formula (7) represents an arylene group, and R ｂ each independently represents a hydrogen atom or a silyl group, i is an integer of 1 to 3, j is an integer of 0 to 2, i+j=3 is satisfied, and k is an integer of 1 to 5). A mesoporous organic silica characterized by containing a group represented by the formula:

6. A mesoporous organic silica, characterized by being a copolymer of the organic silane compound according to any one of claims 1 to 3 and a compound represented by the following formula (8): (Y in the formula (8) represents a divalent to tetravalent organic group, R ｄ each independently represents an alkyl group having 1 to 6 carbon atoms, and each n independently represents an integer of 1 or 2.

7. The following formula (6): [In the formula (6), R is the following formula (7): (X in the formula (7) represents an arylene group, and R ｂ each independently represents a hydrogen atom or a silyl group, i is an integer of 1 to 3, j is an integer of 0 to 2, i+j=3 is satisfied, and k is an integer of 1 to 5). and a group represented by the following formula (9): (Y in the formula (9) represents a divalent to tetravalent organic group, R ｃ each independently represents a hydrogen atom or a silyl group, each l independently represents an integer of 1 to 3, each m independently represents an integer of 1 to 3, and each n independently represents an integer of 1 or 2. and a group represented by the formula:

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