WO2012120905A1 - Crosslinked metallic organic structure and crosslinked organic material, and processes for producing same - Google Patents

Crosslinked metallic organic structure and crosslinked organic material, and processes for producing same Download PDF

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WO2012120905A1
WO2012120905A1 PCT/JP2012/001659 JP2012001659W WO2012120905A1 WO 2012120905 A1 WO2012120905 A1 WO 2012120905A1 JP 2012001659 W JP2012001659 W JP 2012001659W WO 2012120905 A1 WO2012120905 A1 WO 2012120905A1
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organic
metal
mof
crosslinked
organic structure
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French (fr)
Japanese (ja)
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和己 佐田
憲太 小門
拓己 石渡
幸太 杉川
雄基 古川
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国立大学法人北海道大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/06—Potassium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
    • C07F3/06—Zinc compounds

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  • the present invention relates to a crosslinked metal organic structure and a novel covalent organic structure.
  • Covalent organic structures (COF: Covalent-Organic® Framework) and metal organic structures (MOF: Metal-Organic® Framework) are known as organic porous materials with organic skeletons and nano-order pores. ing.
  • a covalent organic structure is a structure in which rigid organic molecules are accumulated by covalent bonds.
  • the metal organic structure is a structure in which organic ligands are accumulated by coordination bonds with metal ions.
  • Non-Patent Document 1 It has been reported that metal organic structures and covalent organic structures have gas storage properties (see Non-Patent Document 1) or catalytic properties (see Non-Patent Document 2). ing. To enhance such properties, the interaction between the structure and its guest molecule is important. In view of this, a contrivance has been proposed to increase the interaction between the structure and its guest molecule by introducing a specific functional group or structure into the organic molecule of the structure.
  • Non-Patent Document 3 an amino group introduced into the skeleton of a covalent organic structure and an isocyanate derivative are reacted (see Non-Patent Document 3), or an acetylene derivative is reacted with an azide group introduced into the skeleton of a metal organic structure. (See Non-Patent Document 4), a method for post-modifying the structure has been proposed.
  • the inventor of the present invention focused on producing a network polymer using a metal organic structure as a template. That is, the organic ligands of the metal organic structure are cross-linked to obtain a cross-linked metal organic structure; and subsequently, metal ions are extracted from the cross-linked metal organic structure to obtain a metal organic structure (MOF). )
  • MOF metal organic structure
  • both the metal organic structure and the covalently bonded organic structure have a problem that they decompose in an acidic solvent and dissolve themselves or lose organic porosity.
  • the skeleton of the metal organic structure is cross-linked by a covalent bond (chemical reaction), so that the material does not decompose even in various solvents.
  • the present inventor has found that an organic cross-linked product prepared by extracting metal ions from a cross-linked metal organic structure is regenerated into a cross-linked metal organic structure by adsorbing metal ions. That is, the present invention provides a new metal ion adsorbent.
  • the first of the present invention relates to a method for producing a crosslinked metal organic structure and an organic crosslinked product shown below.
  • Step A for preparing a metal organic structure containing an organic ligand and a metal ion linking the organic ligand; and cross-linking the ligand with a cross-linking agent;
  • a step B for producing a cross-linked metal organic structure.
  • a method for producing an organic structure wherein the organic ligand has a functional group, and the crosslinking agent has two or more functional groups that can react with the functional group to form a covalent bond.
  • a method of producing a crosslinked organic material comprising: a step B; and a step C of removing a part or all of the metal ions from the crosslinked metal-organic structure.
  • the second of the present invention relates to the following cross-linked metal organic structure and covalent organic structure.
  • a crosslinked metal organic structure comprising an organic ligand, a metal ion that links the organic ligand, and a crosslinking group that bridges the organic ligand.
  • An organic crosslinked product obtained by removing a part or all of the metal ions from the crosslinked metal-organic structure according to [4].
  • the cross-linked organic material according to [5] wherein the cross-linked organic material can become the cross-linked metal organic structure by adsorbing metal ions.
  • a new design policy of a covalently bonded organic structure is provided, and a covalently bonded organic structure having an unprecedented structure can be provided. Furthermore, since the crosslinked organic substance provided by the present invention has a metal ion adsorption ability, it can be applied to a metal recovery raw material.
  • FIG. 5A shows an optical micrograph before immersion (left side) and an optical micrograph after immersion (right side) of sample No. 5 in Table 1;
  • FIG. 6 is a chart showing ATR-IR spectra of metal organic structure N 3 -MOF-15, cross-linked metal organic structure CL-MOF-15, and organic cross-linked substance PG-MOF-15.
  • FIG. 5 is a chart showing XPS spectra of a metal organic structure IR-MOF-9, a crosslinkable metal organic structure CL-MOF-15, and an organic crosslinker PG-MOF-15 that are not reacted with a crosslinking agent.
  • thermogravimetric analysis (TGA) test of the metal organic structure N 3 -MOF-15, the cross-linked metal organic structure CL-MOF-15, and the organic cross-linked product PG-MOF-15 not reacted with the cross-linking agent is shown. It is a graph. ATR-IR of metal organic structure N 3 -MOF-15, cross-linked metal organic structure CL-MOF-15, organic cross-linked body PG-MOF-15 and regenerated cross-linked metal organic structure ReCL-MOF-15 It is a chart figure showing a spectrum. The state in which the cross-linked metal organic structure CL-CD-MOF is changed to the organic cross-linked product PG-CD-MOF in a solvent is observed with an optical microscope.
  • FIG. 5 is a graph showing the degree of swelling of the organic crosslinked product PG-CD-MOF.
  • the horizontal axis represents the concentration of the crosslinking agent L1, and the vertical axis represents the degree of swelling.
  • FIG. 4 is a chart showing FT-IR spectra of metal organic structure CD-MOF, cross-linked metal organic structure CL-CD-MOF, and organic cross-linked product PG-CD-MOF.
  • 2 is a scanning electron microscope image of metal organic structure CD-MOF, cross-linked metal organic structure CL-CD-MOF, and organic cross-linked product PG-CD-MOF.
  • A (b) CD-MOF, (c) (d) CL-CD-MOF, (e) (f) PG-CD-MOF.
  • a ball-and-stick model of CD-MOF (referred to as ( ⁇ -CD) 6) in which 6 molecules of ⁇ -CD are associated.
  • a space-filling model of CD-MOF in which a plurality of ( ⁇ -CD) 6 are associated in a body-centered cubic lattice structure.
  • a metal organic structure 30 can be obtained by reacting an organic ligand 10 and a metal ion 20.
  • the organic ligand 10 has a functional group 11 having reactivity with a crosslinking agent 40 described later.
  • the crosslinkable metal organic structure 50 is obtained by reacting the crosslinker 40 with the functional group 11 of the metal organic structure 30.
  • the organic crosslinked body 60 is a covalent organic structure reflecting the structure of the crosslinked metal organic structure 50. Therefore, when the metal ion 20 is provided to the organic crosslinked body 60, the metal ion 20 is taken in and regenerated into the crosslinked metal organic structure 50.
  • the metal organic structure 30, the cross-linked metal organic structure 50, and the organic cross-linked body 60 will be described in this order.
  • the metal organic structure 30 is obtained by reacting the organic ligand 10 and the metal ion 20.
  • Organic ligand 10 has a molecular structure called “rigid molecule”.
  • a rigid molecule is a molecule in which rotation and bending within the molecule are restricted, and examples thereof include a cyclic molecule, an aromatic ring, or a rod-like molecule in which aromatic rings are connected.
  • Examples of cyclic molecules include cyclodextrins.
  • Examples of the aromatic ring include phenylene, naphthylene, anthracenylene, pentacene, porphyrin, carborane, thiophene, pyridine, C60 and the like.
  • a rigid molecule is obtained by connecting one or more of these aromatic rings.
  • a rigid molecule has a phenylene structure, a diphenylene structure in which two phenylenes are linked, and a terphenylene structure in which three phenylene groups are linked.
  • the organic ligand 10 has two or more functional groups (coordinating functional groups) that can coordinate to metal atoms.
  • functional groups that can be coordinated to a metal atom include a carboxyl group, a pyridinyl group, an amino group, a porphyrinyl group, an acetylacetonate group, a hydroxyl group, a Schiff base, an amino acid residue, and the like.
  • the organic ligand 10 has a functional group 11 having reactivity with a cross-linking agent 40 described later.
  • One functional group 11 may be introduced into the organic ligand 10, or two or more functional groups 11 may be introduced.
  • the kind of the functional group 11 is not particularly limited, and may be an azide group, an amino group, a carboxyl group and analogs thereof, a double bond, a triple bond, an isocyanate group, a hydroxyl group, and the like.
  • the functional group 11 is an azide group, it can be reacted with the crosslinking agent 40 introduced with an acetylene group; if the functional group 11 is an amino group, it can be reacted with the crosslinking agent 40 introduced with an isocyanate group. it can.
  • Examples of the preferred organic ligand 10 include the following compounds.
  • the metal ion 20 is, for example, a metal ion of an actinide element or lanthanide element, and is an ion of a metal element belonging to Group 1 to Group 16 of the periodic table.
  • Specific examples of the metal ion 20 include Li + , Na + , K + , Rb + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 4+ , Zr 4+ , Hf 4+.
  • the organic metal structure 30 is manufactured by, for example, solvothermal reaction of the organic ligand 10 and the metal ion 20 based on a conventional method.
  • the solvothermal reaction is usually carried out in the presence of an acid or base, and the solvent and raw materials are charged from room temperature to high temperature (300 degrees), at atmospheric pressure or in a pressure vessel, and the temperature is raised to the boiling point or higher. The inside pressure is higher than atmospheric pressure.
  • N, N-diethylformamide (DEF) or N, N-dimethylformamide (DMF) is used as a solvent in the solvothermal reaction. This is because they decompose slowly at high temperatures to form amine bases slowly.
  • the conditions for the solvothermal reaction are appropriately set.
  • the metal organic structure 30 preferably has a crystal structure.
  • the metal organic structure 30 is a porous material having nano-order pores. The size of the pores is controlled by the length of the organic ligand 10 (distance between coordination functional groups) and the like.
  • the crosslinkable metal organic structure 50 is obtained by reacting the metal organic structure 30 and the crosslinker 40.
  • the cross-linking agent 40 has two or more groups that react with the functional group 11 introduced into the organic ligand 10 of the metal organic structure 30.
  • the crosslinking agent may be a divalent crosslinking agent or a trivalent or higher crosslinking agent.
  • Specific examples of the crosslinking agent 40 when the functional group 11 is an azide group include the following compounds.
  • the design of the crosslinking agent 40 is performed in consideration of the distance between the functional groups 11 in the metal organic structure 30.
  • the reaction between the metal organic structure 30 and the crosslinking agent 40 is not particularly limited, but is preferably performed under mild conditions. That is, the reaction with the crosslinking agent 40 is completed while maintaining the crystal structure of the metal organic structure 30.
  • the organic cross-linked body 60 is obtained by removing the metal ions 20 from the cross-linked metal organic structure 50.
  • the removal of the metal ion 20 is realized by cutting the coordination bond between the coordination functional group of the organic ligand 10 and the metal ion 20.
  • the coordination functional group of the organic ligand 10 is a carboxyl group
  • the metal ion 20 is dissociated by immersing the cross-linked metal organic structure 50 in a protonated solvent, and the porosity is utilized. It can be removed by washing.
  • a basic solvent may be used in place of the protonated solvent.
  • the proton source of the protonation solvent may be hydrochloric acid, nitric acid or the like.
  • the solvent for the protonated solvent is preferably a mixed solvent of water and an organic solvent. This is because the organic solvent is preferably a good solvent for the crosslinkable metal organic structure 50, whereby the protonated solvent easily penetrates into the crosslinkable metal organic structure 50 and promotes the cleavage of the coordination bond. .
  • the organic cross-linked body 60 can regenerate the cross-linked metal organic structure 50 by adsorbing the metal ions 20.
  • the regenerated crosslinkable metal organic structure 50 is not necessarily the same structure, and crystallinity may be changed.
  • the metal ions 20 to be adsorbed are not necessarily the same ions as the removed metal ions 20 and may be other metal ions.
  • the cross-linked metal organic structure and organic cross-linked product thus produced have voids inside as well as the metal organic structure, and therefore adsorbents of specific molecules other than metal ions in gases and liquids. Can also be used.
  • Toluene was added to the residue obtained by evaporating the solvent under reduced pressure, washed with a saturated aqueous sodium chloride solution, and then dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by column chromatography (silica gel, chloroform) to obtain a yellowish white solid.
  • FIG. 2 shows an ATR-IR spectrum of the metal organic structure N 3 -MOF-15 and an ATR-IR spectrum of sample No. 5 in Table 1. As shown in FIG. 2, in sample No. 5, it can be seen that the peak at 2090 cm ⁇ 1 has disappeared.
  • FIG. 3 shows an optical micrograph of the metal organic structure N 3 -MOF-15 and an optical micrograph of sample No. 5 in Table 1.
  • Sample No. 5 is also a cubic yellow crystal similar to the metal organic structure N 3 -MOF-15.
  • FIG. 4 shows the XRPD pattern of the metal organic structure N 3 -MOF-15 and the XRPD pattern of sample No. 5 in Table 1.
  • any XRPD pattern since the peaks are coincident, it can be understood that the crosslinking reaction has progressed while maintaining the crystal structure.
  • FIG. 5A shows an optical micrograph before immersion (left side) and an optical micrograph after immersion (right side) of sample No. 5 in Table 1. As shown in FIG. 5A, it can be seen that the volume is increased by about 4.34 times due to swelling by immersion.
  • FIG. 5B shows an optical micrograph before immersion (left side) and an optical micrograph after immersion (right side) of sample No. 7 in Table 1. As shown in FIG. 5B, it can be seen that the volume is increased by about 2.37 times due to swelling by immersion.
  • the swelling ratios of No5, No7 and No8 are shown in the following table. As shown in Table 2, it was suggested that the higher the concentration of the crosslinking agent during the crosslinking reaction, the higher the swelling ratio (Comparison between No5 and No7 to No8). When the concentration of the crosslinking agent is too high, it is considered that the crosslinking rate is lowered because the ligands of the metal structure cannot be crosslinked by the crosslinking agent.
  • FIG. 6 shows a metal organic structure not reacted with a crosslinking agent (reference sample; metal organic structure composed of 4,4′-biphenyldicarboxylic acid and zinc ions), and a crosslinked metal organic structure CL-MOF-15.
  • 2 shows an ATR-IR spectrum of the organic crosslinked product PG-MOF-15.
  • a peak around 1390 to 1400 cm ⁇ 1 observed with the metal organic structure N 3 -MOF-15 and the crosslinked metal organic structure CL-MOF-15 C—O It can be seen that (surface deflection) has disappeared.
  • FIG. 7 shows a metal organic structure IR-MOF-9 that is not reacted with a crosslinking agent (a metal organic structure synthesized by using a dicarboxylic acid having a biphenyl group as a linker and zinc ions as metal ions), a crosslinked type 2 shows XPS spectra of metal-organic structure CL-MOF-15 and organic crosslinked product PG-MOF-15.
  • the XPS spectrum was observed by using a sample substrate cast / dried on an indium substrate as a measurement substrate. As shown in FIG.
  • FIG. 8 shows guests of the metal organic structure N 3 -MOF-15, the cross-linked metal organic structure CL-MOF-15, and the organic cross-linked product PG-MOF-15 that were not reacted with the cross-linking agent (diethyl as a solvent).
  • the results of a thermogravimetric analysis (TGA) test to evaluate the inclusion ability of formamide DEF) are shown.
  • the thermogravimetric analysis (TGA) test was performed under the conditions of a sample amount of about 5 mg, a measurement temperature region of 30 to 500 ° C., a temperature rising rate of 3.0 ° C./min, and a nitrogen gas flow rate of 200 ml / min.
  • the first mass decrease occurs rapidly from 30 ° C. to 150 ° C .; the second mass decrease occurs near 200 ° C .; from 380 ° C. to 450 ° C.
  • a third mass loss has occurred.
  • the first decrease in mass appears to be caused by the removal of the guest solvent diethylformamide.
  • the second mass loss is believed to be due to the decomposition of the azido group.
  • the third mass loss is believed to be due to the decomposition of the structural skeleton itself.
  • the second mass reduction (around 200 ° C.) is not observed. This is probably because the crosslinked metal organic structure CL-MOF-15 has no azide group. Further, the first mass decrease in the mass curve of the cross-linked metal organic structure CL-MOF-15 is less than the first mass decrease in the mass curve of the metal organic structure N 3 -MOF-15. This is presumably because the volume of pores in the cross-linked metal organic structure CL-MOF-15 is reduced by cross-linking.
  • Regeneration from crosslinked organic material PG-MOF-15 to crosslinked metal organic structure CL-MOF-15 Re-coordination of zinc ions to crosslinked organic material PG-MOF-15 from which metal ions (zinc ions) have been removed Thus, it was regenerated into a cross-linked metal organic structure CL-MOF-15.
  • the regenerated crosslinked organic metal structure is called ReCL-MOF-15.
  • the metal was re-coordinated under the conditions shown in Table 3. Specifically, for example, in No. 2 in the table below, the organic crosslinked product PG-MOF-15 was infiltrated into a 0.25 mM zinc nitrate hexahydrate / DEF solution and allowed to stand at 80 ° C. for 36 hours.
  • FIG. 9 shows metal organic structure N 3 -MOF-15, cross-linked metal organic structure CL-MOF-15, organic cross-linked body PG-MOF-15, and regenerated cross-linked metal organic structure ReCL-MOF- 15 ATR-IR spectra are shown.
  • Example 2 Synthesis of metal organic structure CD-MOF ([(C 48 H 80 O 40 ) (KOH) 2 ] n.) ⁇ -cyclodextrin ( ⁇ -CD) represented by the following structural formula is the smallest structural unit, A CD-MOF having a structure in which ⁇ -CD is regularly and three-dimensionally associated by a coordinate bond between a hydroxyl group of ⁇ -CD and a potassium ion was synthesized.
  • the composition formula of CD-MOF is represented by [(C 48 H 80 O 40 ) (KOH) 2 ] n. Specifically, it was synthesized according to the method described in Angew. Chem. Int. Ed. 2010, 49, 8630.
  • FIG. 14 shows a ball-and-stick model of CD-MOF (referred to as ( ⁇ -CD) 6) in which six molecules of ⁇ -CD are associated, and CD in which a plurality of ( ⁇ -CD) 6 are associated in a body-centered cubic lattice structure
  • ⁇ -CD CD-MOF
  • metal organic structure CD-MOF 20 mg is taken in a sample of the synthesis of cross-linked metal organic structure CL-CD-MOF, and ethylene glycol diglycidyl ether (crosslinking agent L1) / ethanol solution at a concentration of 1.5 to 5.0 M And allowed to stand at 65 ° C. for 3 days to carry out an internal crosslinking reaction to obtain a crosslinked metal organic structure CL-CD-MOF as transparent crystals.
  • FIG. 10 shows a state in which the cross-linked metal organic structure CL-CD-MOF is changed to the organic cross-linked product PG-CD-MOF in a solvent, as observed with an optical microscope. The shape did not change, only the size changed due to swelling.
  • FIG. 11 shows the degree of swelling of the organic crosslinked product PG-CD-MOF obtained by carrying out an internal crosslinking reaction in various concentration regions of the crosslinking agent L1 and removing the coordination of potassium ions.
  • L PG-CD-MOF represents the length of one side of the crystal of the organic crosslinked product PG-CD-MOF
  • L CL-CD-MOF represents the length of one side of the crosslinked metal-organic structure CL-CD-MOF.
  • the concentration of the crosslinking agent L1 is 1.5 to 2.0M
  • the degree of swelling is the lowest, indicating that the crosslinking reaction proceeds at the highest density. Thereafter, the experiment was conducted with the concentration of the cross-linking agent L1 unified at 1.5M.
  • FIG. 12 shows the result of measuring the FT-IR spectrum of the cross-linked metal organic structure CL-CD-MOF produced by the cross-linking agent L1.
  • the stretching intensity of C—O—C derived from ⁇ -CD (1150-1120 cm-1) is broad, and the peak intensity derived from the methylene chain due to modification of the crosslinking agent L1 (2920-2850 cm-1) was confirmed to increase. From this, it is thought that the crosslinking agent L1 is reacting as expected.
  • the metal organic structure CD-MOF which is a crystal has a cubic shape
  • the crosslinked metal organic structure CL-CD-MOF which is a product of the crosslinking reaction and the organic compound crosslinked body PG-CD-MOF after hydrolysis Both of them were found to maintain the form of the metal organic structure CD-MOF.
  • the dried sample In addition to the sample swollen with the solvent, the dried sample also had a structure with linear sides and vertices derived from the crystals from which the organic crosslinked product PG-CD-MOF was derived.
  • a new design policy of a covalently bonded organic structure is provided, and a covalently bonded organic structure having an unprecedented structure can be provided. Furthermore, since the organic cross-linked product provided by the present invention has a metal ion adsorption ability, it can be applied to a metal recovery raw material such as metal ions or a sustained release system of a drug.

Abstract

Provided is a process for producing a novel crosslinked organic material, which relies on the idea of producing a covalently bonded organic structure that reflects the structure of a metallic organic structure. Provided is a process for producing a crosslinked organic material, comprising: a step (A) of preparing a metallic organic structure comprising organic ligands and metal ions that connect the organic ligands; a step (B) of crosslinking the ligands with a crosslinking agent to produce a crosslinked metallic organic structure; and a step (C) removing at least some of the metal ions from the crosslinked metallic organic structure.

Description

架橋型金属有機構造体および有機物架橋体、およびそれらの製造方法Cross-linked metal-organic structure, organic cross-linked body, and production method thereof
　本発明は、架橋型金属有機構造体および共有結合性の新規有機構造体に関する。 The present invention relates to a crosslinked metal organic structure and a novel covalent organic structure.
　有機物を基本骨格にもち、ナノオーダーの空孔を有する有機多孔性物質として、共有結合性有機構造体（ＣＯＦ：Covalent-Organic Framework）および金属有機構造体（ＭＯＦ：Metal-Organic Framework）が知られている。共有結合性有機構造体は、剛直な有機分子を共有結合により集積させた構造体である。一方、金属有機構造体は、有機配位子を金属イオンとの配位結合で集積させた構造体である。 Covalent organic structures (COF: Covalent-Organic® Framework) and metal organic structures (MOF: Metal-Organic® Framework) are known as organic porous materials with organic skeletons and nano-order pores. ing. A covalent organic structure is a structure in which rigid organic molecules are accumulated by covalent bonds. On the other hand, the metal organic structure is a structure in which organic ligands are accumulated by coordination bonds with metal ions.
　金属有機構造体や共有結合性有機構造体は、ガス吸蔵特性を有していたり（非特許文献１を参照）、触媒特性を有していたりする（非特許文献２を参照）ことが報告されている。そのような特性を高めるには、構造体とそのゲスト分子との相互作用が重要である。そこで、構造体の有機分子に特定の官能基や構造を導入することで、構造体とそのゲスト分子との相互作用を高めようとする工夫が提案されている。 It has been reported that metal organic structures and covalent organic structures have gas storage properties (see Non-Patent Document 1) or catalytic properties (see Non-Patent Document 2). ing. To enhance such properties, the interaction between the structure and its guest molecule is important. In view of this, a contrivance has been proposed to increase the interaction between the structure and its guest molecule by introducing a specific functional group or structure into the organic molecule of the structure.
　例えば、共有結合性有機構造体の骨格に導入したアミノ基と、イソシアネート誘導体とを反応させたり（非特許文献３を参照）、金属有機構造体の骨格に導入したアジド基にアセチレン誘導体を反応させたりして（非特許文献４を参照）、構造体を事後修飾する手法が提案されている。 For example, an amino group introduced into the skeleton of a covalent organic structure and an isocyanate derivative are reacted (see Non-Patent Document 3), or an acetylene derivative is reacted with an azide group introduced into the skeleton of a metal organic structure. (See Non-Patent Document 4), a method for post-modifying the structure has been proposed.
　本発明者は、金属有機構造体を鋳型としてネットワークポリマーを作製することに着目した。すなわち、金属有機構造体の有機配位子間を架橋させて、架橋型金属有機構造体を得て；続いて、架橋型金属有機構造体から金属イオンを引き抜くことで、金属有機構造体（ＭＯＦ）構造を反映した新たな共有結合性の有機構造体（以下、有機物架橋体という）を作製するに至った。 The inventor of the present invention focused on producing a network polymer using a metal organic structure as a template. That is, the organic ligands of the metal organic structure are cross-linked to obtain a cross-linked metal organic structure; and subsequently, metal ions are extracted from the cross-linked metal organic structure to obtain a metal organic structure (MOF). ) A new covalent organic structure reflecting the structure (hereinafter referred to as an organic cross-linked product) has been produced.
　つまり、金属有機構造体および共有結合性有機構造体とも、酸性溶媒中などで分解し、それ自体が溶解してしまったり、有機多孔性を喪失したりするという問題点があった。これに対して本発明では、金属有機構造体の骨格を、共有結合(化学反応)によって架橋することで、様々な溶媒中でも分解しない材料とする。 That is, both the metal organic structure and the covalently bonded organic structure have a problem that they decompose in an acidic solvent and dissolve themselves or lose organic porosity. In contrast, in the present invention, the skeleton of the metal organic structure is cross-linked by a covalent bond (chemical reaction), so that the material does not decompose even in various solvents.
　さらに本発明者は、架橋型金属有機構造体から金属イオンを引き抜いて作製した有機物架橋体は、金属イオンを吸着することで、架橋型金属有機構造体に再生されることを見出した。つまり、本発明は新しい金属イオン吸着体を提供する。 Furthermore, the present inventor has found that an organic cross-linked product prepared by extracting metal ions from a cross-linked metal organic structure is regenerated into a cross-linked metal organic structure by adsorbing metal ions. That is, the present invention provides a new metal ion adsorbent.
　すなわち本発明の第一は、以下に示す架橋型金属有機構造体および有機物架橋体の製造方法に関する。
　［１］有機配位子と、前記有機配位子を連結する金属イオンを含む金属有機構造体を用意するステップＡと；前記配位子を架橋剤で架橋して架橋型金属有機構造体とするステップＢとを有する、架橋型金属有機構造体の製造方法。
　［２］前記有機配位子は官能基を有し、かつ前記架橋剤は、前記官能基と反応して共有結合を形成できる２以上の官能基を有する、［１］に記載の架橋型金属有機構造体の製造方法。
　［３］有機配位子と、前記有機配位子を連結する金属イオンを含む金属有機構造体を用意するステップＡと；前記配位子を架橋剤で架橋して架橋型金属有機構造体とするステップＢと；前記架橋型金属有機構造体から、前記金属イオンのうちの一部または全部を除去するステップＣとを有する、有機物架橋体を製造する方法。 That is, the first of the present invention relates to a method for producing a crosslinked metal organic structure and an organic crosslinked product shown below.
[1] Step A for preparing a metal organic structure containing an organic ligand and a metal ion linking the organic ligand; and cross-linking the ligand with a cross-linking agent; A step B for producing a cross-linked metal organic structure.
[2] The crosslinked metal according to [1], wherein the organic ligand has a functional group, and the crosslinking agent has two or more functional groups that can react with the functional group to form a covalent bond. A method for producing an organic structure.
[3] Step A of preparing an organic ligand and a metal organic structure containing a metal ion linking the organic ligand; and cross-linking the ligand with a cross-linking agent; A method of producing a crosslinked organic material, comprising: a step B; and a step C of removing a part or all of the metal ions from the crosslinked metal-organic structure.
　本発明の第二は、以下に示す架橋型金属有機構造体および共有結合性有機構造体に関する。
　［４］有機配位子と、前記有機配位子を連結する金属イオンと、前記有機配位子を架橋する架橋基とを含む、架橋型金属有機構造体。
　［５］前記［４］に記載の架橋型金属有機構造体から、前記金属イオンのうちの一部または全部を除去して得られる、有機物架橋体。
　［６］前記有機物架橋体は、金属イオンを吸着することで前記架橋型金属有機構造体となることができる、［５］に記載の有機物架橋体。 The second of the present invention relates to the following cross-linked metal organic structure and covalent organic structure.
[4] A crosslinked metal organic structure comprising an organic ligand, a metal ion that links the organic ligand, and a crosslinking group that bridges the organic ligand.
[5] An organic crosslinked product obtained by removing a part or all of the metal ions from the crosslinked metal-organic structure according to [4].
[6] The cross-linked organic material according to [5], wherein the cross-linked organic material can become the cross-linked metal organic structure by adsorbing metal ions.
　本発明により、共有結合性有機構造体の新しい設計方針が提供され、これまでにない構造を有する共有結合性の有機構造体の提供が可能となる。さらには、本発明により提供される有機物架橋体は、金属イオン吸着能を有するので、金属回収原料への応用なども可能である。 According to the present invention, a new design policy of a covalently bonded organic structure is provided, and a covalently bonded organic structure having an unprecedented structure can be provided. Furthermore, since the crosslinked organic substance provided by the present invention has a metal ion adsorption ability, it can be applied to a metal recovery raw material.
架橋型金属有機構造体および共有結合性有機構造体の製造プロセスの概略を示す図である。It is a figure which shows the outline of the manufacturing process of a bridge | crosslinking type metal organic structure and a covalent bond organic structure. 金属有機構造体Ｎ３－ＭＯＦ－１５のＡＴＲ－ＩＲスペクトルと、表１のサンプルＮｏ５のＡＴＲ－ＩＲスペクトルとを示すチャートである。2 is a chart showing an ATR-IR spectrum of metal organic structure N 3 -MOF-15 and an ATR-IR spectrum of sample No. 5 in Table 1. FIG. 金属有機構造体Ｎ３－ＭＯＦ－１５の光学顕微鏡写真と、表１のサンプルＮｏ５の光学顕微鏡写真である。They are an optical micrograph of metal organic structure N 3 -MOF-15 and an optical micrograph of sample No. 5 in Table 1. 金属有機構造体Ｎ３－ＭＯＦ－１５のＸＲＰＤパターンと、表１のサンプルＮｏ５のＸＲＰＤパターンとを示すチャート図である。2 is a chart showing an XRPD pattern of a metal organic structure N 3 -MOF-15 and an XRPD pattern of sample No. 5 in Table 1. FIG. 図５Ａには、表１のサンプルＮｏ５の、浸漬前の光学顕微鏡写真（左側）と、浸漬後の光学顕微鏡写真（右側）が示され；図５Ｂには、表１のサンプルＮｏ７の、浸漬前の光学顕微鏡写真（左側）と、浸漬後の光学顕微鏡写真（右側）が示される。FIG. 5A shows an optical micrograph before immersion (left side) and an optical micrograph after immersion (right side) of sample No. 5 in Table 1; FIG. An optical micrograph (left side) and an optical micrograph after immersion (right side) are shown. 金属有機構造体Ｎ３－ＭＯＦ－１５、架橋型金属有機構造体ＣＬ－ＭＯＦ－１５および有機物架橋体ＰＧ－ＭＯＦ－１５の、ＡＴＲ－ＩＲスペクトルを示すチャート図である。FIG. 6 is a chart showing ATR-IR spectra of metal organic structure N 3 -MOF-15, cross-linked metal organic structure CL-MOF-15, and organic cross-linked substance PG-MOF-15. 架橋剤と反応させていない金属有機構造体ＩＲ－ＭＯＦ－９、架橋型金属有機構造体ＣＬ－ＭＯＦ－１５および有機物架橋体ＰＧ－ＭＯＦ－１５の、ＸＰＳスペクトルを示すチャート図である。FIG. 5 is a chart showing XPS spectra of a metal organic structure IR-MOF-9, a crosslinkable metal organic structure CL-MOF-15, and an organic crosslinker PG-MOF-15 that are not reacted with a crosslinking agent. 架橋剤と反応させていない金属有機構造体Ｎ３－ＭＯＦ－１５、架橋型金属有機構造体ＣＬ－ＭＯＦ－１５および有機物架橋体ＰＧ－ＭＯＦ－１５の熱重量分析（ＴＧＡ）試験の結果を示すグラフである。The result of the thermogravimetric analysis (TGA) test of the metal organic structure N 3 -MOF-15, the cross-linked metal organic structure CL-MOF-15, and the organic cross-linked product PG-MOF-15 not reacted with the cross-linking agent is shown. It is a graph. 金属有機構造体Ｎ３－ＭＯＦ－１５、架橋型金属有機構造体ＣＬ－ＭＯＦ－１５、有機物架橋体ＰＧ－ＭＯＦ－１５および再生された架橋型金属有機構造体ＲｅＣＬ－ＭＯＦ－１５のＡＴＲ－ＩＲスペクトルを示すチャート図である。ATR-IR of metal organic structure N 3 -MOF-15, cross-linked metal organic structure CL-MOF-15, organic cross-linked body PG-MOF-15 and regenerated cross-linked metal organic structure ReCL-MOF-15 It is a chart figure showing a spectrum. 架橋型金属有機構造体ＣＬ－ＣＤ－ＭＯＦが、溶媒中で有機物架橋体ＰＧ－ＣＤ－ＭＯＦに変化する様子を光学顕微鏡で観察したものである。The state in which the cross-linked metal organic structure CL-CD-MOF is changed to the organic cross-linked product PG-CD-MOF in a solvent is observed with an optical microscope. 有機物架橋体ＰＧ－ＣＤ－ＭＯＦの膨潤度を示すグラフである。横軸は架橋剤Ｌ１の濃度、縦軸は膨潤度を示す。5 is a graph showing the degree of swelling of the organic crosslinked product PG-CD-MOF. The horizontal axis represents the concentration of the crosslinking agent L1, and the vertical axis represents the degree of swelling. 金属有機構造体ＣＤ－ＭＯＦ、架橋型金属有機構造体ＣＬ－ＣＤ－ＭＯＦ、有機物架橋体ＰＧ－ＣＤ－ＭＯＦのＦＴ－ＩＲスペクトルを示すチャート図である。FIG. 4 is a chart showing FT-IR spectra of metal organic structure CD-MOF, cross-linked metal organic structure CL-CD-MOF, and organic cross-linked product PG-CD-MOF. 金属有機構造体ＣＤ－ＭＯＦ、架橋型金属有機構造体ＣＬ－ＣＤ－ＭＯＦ、有機物架橋体ＰＧ－ＣＤ－ＭＯＦの走査型電子顕微鏡像である。（ａ）（ｂ）ＣＤ－ＭＯＦ、（ｃ）（ｄ）ＣＬ－ＣＤ－ＭＯＦ、（ｅ）（ｆ）ＰＧ－ＣＤ－ＭＯＦ。2 is a scanning electron microscope image of metal organic structure CD-MOF, cross-linked metal organic structure CL-CD-MOF, and organic cross-linked product PG-CD-MOF. (A) (b) CD-MOF, (c) (d) CL-CD-MOF, (e) (f) PG-CD-MOF. ６分子のγ－ＣＤが会合したＣＤ－ＭＯＦ（（γ－ＣＤ）６と称する）のボールアンドスティックモデル。A ball-and-stick model of CD-MOF (referred to as (γ-CD) 6) in which 6 molecules of γ-CD are associated. 複数の（γ－ＣＤ）６が体心立方格子構造で会合したＣＤ－ＭＯＦの空間充填モデル。A space-filling model of CD-MOF in which a plurality of (γ-CD) 6 are associated in a body-centered cubic lattice structure.
　まず初めに、本発明の架橋型金属有機構造体および有機物架橋体の製造プロセスの概略を、図１を参照して説明する。 First, the outline of the production process of the cross-linked metal organic structure and organic cross-linked product of the present invention will be described with reference to FIG.
　図１に示されるように、有機配位子１０と、金属イオン２０とを反応させることで、金属有機構造体３０を得ることができる。有機配位子１０は、後述の架橋剤４０との反応性を有する官能基１１を有している。金属有機構造体３０の官能基１１に架橋剤４０を反応させることで、架橋型金属有機構造体５０が得られる。 As shown in FIG. 1, a metal organic structure 30 can be obtained by reacting an organic ligand 10 and a metal ion 20. The organic ligand 10 has a functional group 11 having reactivity with a crosslinking agent 40 described later. The crosslinkable metal organic structure 50 is obtained by reacting the crosslinker 40 with the functional group 11 of the metal organic structure 30.
　架橋型金属有機構造体５０から金属イオン２０を引き抜く（除去する）と、有機物架橋体６０が得られる。有機物架橋体６０は、架橋型金属有機構造体５０の構造を反映した共有結合性の有機構造体である。そのため、有機物架橋体６０に金属イオン２０を提供すると、金属イオン２０を取り込んで、架橋型金属有機構造体５０に再生する。 When the metal ions 20 are extracted (removed) from the cross-linked metal organic structure 50, the organic cross-linked body 60 is obtained. The organic crosslinked body 60 is a covalent organic structure reflecting the structure of the crosslinked metal organic structure 50. Therefore, when the metal ion 20 is provided to the organic crosslinked body 60, the metal ion 20 is taken in and regenerated into the crosslinked metal organic structure 50.
　以下において、金属有機構造体３０と、架橋型金属有機構造体５０と、有機物架橋体６０の順に説明する。 Hereinafter, the metal organic structure 30, the cross-linked metal organic structure 50, and the organic cross-linked body 60 will be described in this order.
　金属有機構造体３０について
　前述の通り、金属有機構造体３０は、有機配位子１０と、金属イオン２０とを反応させることで得られる。 About Metal Organic Structure 30 As described above, the metal organic structure 30 is obtained by reacting the organic ligand 10 and the metal ion 20.
　有機配位子１０は、いわゆる「剛直分子」と称される分子構造を有する。剛直分子とは、分子内の回転や屈曲が制限されている分子であり、環状分子や芳香環または芳香環が連結した棒状分子が挙げられる。環状分子の例にはシクロデキストリンが挙げられる。芳香環の例には、フェニレン、ナフチレン、アントラセニレン、ペンタセン、ポルフィリン、カルボラン、チオフェン、ピリジン、Ｃ６０などが含まれる。例えば、剛直分子は、これらの芳香環を１つまたは２つ以上連結したものである。例えば剛直分子は、フェニレン構造、２つのフェニレンが連結したジフェニレン構造、３つのフェニレン基が連結したターフェニレン構造を有する。 Organic ligand 10 has a molecular structure called “rigid molecule”. A rigid molecule is a molecule in which rotation and bending within the molecule are restricted, and examples thereof include a cyclic molecule, an aromatic ring, or a rod-like molecule in which aromatic rings are connected. Examples of cyclic molecules include cyclodextrins. Examples of the aromatic ring include phenylene, naphthylene, anthracenylene, pentacene, porphyrin, carborane, thiophene, pyridine, C60 and the like. For example, a rigid molecule is obtained by connecting one or more of these aromatic rings. For example, a rigid molecule has a phenylene structure, a diphenylene structure in which two phenylenes are linked, and a terphenylene structure in which three phenylene groups are linked.
　有機配位子１０は、金属原子に配位可能な官能基（配位官能基）を２以上有する。金属原子に配位可能な官能基の例には、カルボキシル基、ピリジニル基、アミノ基、ポルフィリニル基、アセチルアセトナート基、水酸基、シッフ塩基、アミノ酸残基などが含まれる。 The organic ligand 10 has two or more functional groups (coordinating functional groups) that can coordinate to metal atoms. Examples of functional groups that can be coordinated to a metal atom include a carboxyl group, a pyridinyl group, an amino group, a porphyrinyl group, an acetylacetonate group, a hydroxyl group, a Schiff base, an amino acid residue, and the like.
　さらに、有機配位子１０は、後述の架橋剤４０との反応性を有する官能基１１を有している。有機配位子１０には、１つの官能基１１が導入されていてもよいし、２以上の官能基１１が導入されていてもよい。官能基１１の種類は特に限定されず、アジド基、アミノ基、カルボキシル基およびその類縁体、二重結合、三重結合、イソシアナート基、水酸基などでありうる。例えば、官能基１１がアジド基であれば、アセチレン基を導入した架橋剤４０と反応させることができ；官能基１１がアミノ基であれば、イソシアネート基を導入した架橋剤４０と反応させることができる。 Furthermore, the organic ligand 10 has a functional group 11 having reactivity with a cross-linking agent 40 described later. One functional group 11 may be introduced into the organic ligand 10, or two or more functional groups 11 may be introduced. The kind of the functional group 11 is not particularly limited, and may be an azide group, an amino group, a carboxyl group and analogs thereof, a double bond, a triple bond, an isocyanate group, a hydroxyl group, and the like. For example, if the functional group 11 is an azide group, it can be reacted with the crosslinking agent 40 introduced with an acetylene group; if the functional group 11 is an amino group, it can be reacted with the crosslinking agent 40 introduced with an isocyanate group. it can.
　好ましい有機配位子１０の例には、以下の化合物が含まれる。
Figure JPOXMLDOC01-appb-C000001
 Examples of the preferred organic ligand 10 include the following compounds.
Figure JPOXMLDOC01-appb-C000001
　金属イオン２０は、例えば、アクチニド元素やランタニド元素の金属イオンであり、元素周期表の第１族～第１６族の金属元素のイオンである。金属イオン２０の具体例には、Ｌｉ＋、Ｎａ＋、Ｋ＋、Ｒｂ＋、Ｂｅ２＋、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋、Ｂａ２＋、Ｓｃ３＋、Ｙ３＋、Ｔｉ４＋、Ｚｒ４＋、Ｈｆ４＋、Ｖ４＋、Ｖ３＋、Ｖ２＋、Ｎｂ３＋、Ｔａ３＋、Ｃｒ３＋、Ｍｏ３＋、Ｗ３＋、Ｍｎ３＋、Ｍｎ２＋、Ｒｅ３＋、Ｒｅ２＋、Ｆｅ３＋、Ｆｅ２＋、Ｒｕ３＋、Ｒｕ２＋、Ｏｓ３＋、Ｏｓ２＋、Ｃｏ３＋、Ｃｏ２＋、Ｒｈ２＋、Ｒｈ＋、Iｒ２＋、Iｒ＋、Ｎｉ２＋、Ｎｉ＋、Ｐｄ２＋、Ｐｄ＋、Ｐｔ２＋、Ｐｔ＋、Ｃｕ２＋、Ｃｕ＋、Ａｇ＋、Ａｕ＋、Ｚｎ２＋、Ｃｄ２＋、Ｈｇ２＋、Ａｌ３＋、Ｇａ３＋、Iｎ３＋、Ｔｌ３＋、Ｓｉ４＋、Ｓｉ２＋、Ｇｅ４＋、Ｇｅ２＋、Ｓｎ４＋、Ｓｎ２＋、Ｐｂ４＋、Ｐｂ２＋、Ａｓ５＋、Ａｓ３＋、Ａｓ＋、Ｓｂ５＋、Ｓｂ３＋、Ｓｂ＋、Ｂｉ５＋、Ｂｉ３＋、Ｂｉ＋及びこれらの組み合わせが含まれる。 The metal ion 20 is, for example, a metal ion of an actinide element or lanthanide element, and is an ion of a metal element belonging to Group 1 to Group 16 of the periodic table. Specific examples of the metal ion 20 include Li + , Na + , K + , Rb + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 4+ , Zr 4+ , Hf 4+. , V 4+ , V 3+ , V 2+ , Nb 3+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Mn 2+ , Re 3+ , Re 2+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Ru 2+ , 3+ , Os 2+ , Co 3+ , Co 2+ , Rh 2+ , Rh + , Ir 2+ , Ir + , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Ag + , au +, Zn 2+, Cd 2+ , Hg 2+, Al 3+, Ga 3+, In 3+, Tl 3+, Si 4+, Si 2+, Ge 4+, Ge 2+, Sn 4+ Sn 2+, Pb 4+, Pb 2+ , As 5+, As 3+, As +, Sb 5+, Sb 3+, Sb +, Bi 5+, Bi 3+, include Bi +, and combinations thereof.
　有機配位子１０と金属イオン２０とを、定法に基づいて例えばソルボサーマル反応させることで、金属有機構造体３０が製造される。ソルボサーマル反応は、通常、酸または塩基の存在下で行われ、常温から高温(３００度)まで、大気圧下または圧力容器中に溶媒と原料を投入し、沸点温度以上まで昇温し、容器内の圧力が大気圧以上の条件で行う。ソルボサーマル反応における溶媒として、また、水以外のＮ,Ｎ-ジエチルホルムアミド（ＤＥＦ）またはＮ,Ｎ-ジメチルホルムアミド（ＤＭＦ）が用いられる。これらは高温で分解して緩やかにアミン塩基を生成するからである。ソルボサーマル反応の条件は、適宜設定される。 The organic metal structure 30 is manufactured by, for example, solvothermal reaction of the organic ligand 10 and the metal ion 20 based on a conventional method. The solvothermal reaction is usually carried out in the presence of an acid or base, and the solvent and raw materials are charged from room temperature to high temperature (300 degrees), at atmospheric pressure or in a pressure vessel, and the temperature is raised to the boiling point or higher. The inside pressure is higher than atmospheric pressure. As a solvent in the solvothermal reaction, N, N-diethylformamide (DEF) or N, N-dimethylformamide (DMF) other than water is used. This is because they decompose slowly at high temperatures to form amine bases slowly. The conditions for the solvothermal reaction are appropriately set.
　金属有機構造体３０は、結晶構造を有していることが好ましい。また、金属有機構造体３０は、ナノオーダーの空孔を有する多孔性物質である。空孔のサイズは、有機配位子１０の長さ（配位官能基同士の距離）などによって制御される。 The metal organic structure 30 preferably has a crystal structure. The metal organic structure 30 is a porous material having nano-order pores. The size of the pores is controlled by the length of the organic ligand 10 (distance between coordination functional groups) and the like.
　架橋型金属有機構造体５０について
　架橋型金属有機構造体５０は、金属有機構造体３０と架橋剤４０とを反応させることで得られる。架橋剤４０は、金属有機構造体３０の有機配位子１０に導入された官能基１１と反応する基を２以上有する。架橋剤は、二価性架橋剤であってもよく、三価性以上の架橋剤であってもよい。官能基１１がアジド基である場合の、架橋剤４０の具体例には以下の化合物が含まれる。
Figure JPOXMLDOC01-appb-C000002
 About Crosslinkable Metal Organic Structure 50 The crosslinkable metal organic structure 50 is obtained by reacting the metal organic structure 30 and the crosslinker 40. The cross-linking agent 40 has two or more groups that react with the functional group 11 introduced into the organic ligand 10 of the metal organic structure 30. The crosslinking agent may be a divalent crosslinking agent or a trivalent or higher crosslinking agent. Specific examples of the crosslinking agent 40 when the functional group 11 is an azide group include the following compounds.
Figure JPOXMLDOC01-appb-C000002
　架橋剤４０の設計は、金属有機構造体３０における官能基１１同士の距離を考慮して行う。 The design of the crosslinking agent 40 is performed in consideration of the distance between the functional groups 11 in the metal organic structure 30.
　金属有機構造体３０と架橋剤４０との反応は特に限定されないが、好ましくは温和な条件で行う。つまり、金属有機構造体３０の結晶構造を維持したまま、架橋剤４０との反応を完結させる。 The reaction between the metal organic structure 30 and the crosslinking agent 40 is not particularly limited, but is preferably performed under mild conditions. That is, the reaction with the crosslinking agent 40 is completed while maintaining the crystal structure of the metal organic structure 30.
　有機物架橋体６０について
　有機物架橋体６０は、架橋型金属有機構造体５０から金属イオン２０を除去することにより得られる。金属イオン２０の除去は、有機配位子１０の配位官能基と金属イオン２０との配位結合を切断することで実現される。有機配位子１０の配位官能基がカルボキシル基である場合には、架橋型金属有機構造体５０をプロトン化溶媒に浸漬することで、金属イオン２０を解離させ、多孔質性を利用して洗浄することにより除去することができる。プロトン化溶媒の代わりに塩基性溶媒を用いてもよい。また、キレート剤（ＥＤＴＡなど）などの、金属イオンと錯体を形成する化合物と反応させて、架橋型金属有機構造体５０から金属イオン２０を除去することも考えられる。 Regarding Organic Cross-Linked Body 60 The organic cross-linked body 60 is obtained by removing the metal ions 20 from the cross-linked metal organic structure 50. The removal of the metal ion 20 is realized by cutting the coordination bond between the coordination functional group of the organic ligand 10 and the metal ion 20. When the coordination functional group of the organic ligand 10 is a carboxyl group, the metal ion 20 is dissociated by immersing the cross-linked metal organic structure 50 in a protonated solvent, and the porosity is utilized. It can be removed by washing. A basic solvent may be used in place of the protonated solvent. It is also conceivable to remove the metal ion 20 from the cross-linked metal organic structure 50 by reacting with a compound that forms a complex with the metal ion, such as a chelating agent (such as EDTA).
　プロトン化溶媒のプロトン源は、塩酸、硝酸などであればよい。プロトン化溶媒の溶媒は、水と有機溶媒との混合溶媒であることが好ましい。有機溶媒は、架橋型金属有機構造体５０の良溶媒であることが好ましく、それによりプロトン化溶媒が架橋型金属有機構造体５０に浸透しやすくなり、配位結合の切断を促進するからである。 The proton source of the protonation solvent may be hydrochloric acid, nitric acid or the like. The solvent for the protonated solvent is preferably a mixed solvent of water and an organic solvent. This is because the organic solvent is preferably a good solvent for the crosslinkable metal organic structure 50, whereby the protonated solvent easily penetrates into the crosslinkable metal organic structure 50 and promotes the cleavage of the coordination bond. .
　有機物架橋体６０は、金属イオン２０を吸着して、架橋型金属有機構造体５０を再生することができることが好ましい。再生された架橋性金属有機構造体５０は、必ずしも同一の構造体である必要はなく、結晶性が変わっていたりしてもよい。吸着させる金属イオン２０も、除去された金属イオン２０と必ずしも同一のイオンである必要はなく、他の金属イオンであっても構わない。また、このようにして作られた架橋型金属有機構造体や有機物架橋体は金属有機構造体と同様に内部に空隙を持つことから、気体中や液体中の金属イオン以外の特定分子の吸着剤としても使用できる。 It is preferable that the organic cross-linked body 60 can regenerate the cross-linked metal organic structure 50 by adsorbing the metal ions 20. The regenerated crosslinkable metal organic structure 50 is not necessarily the same structure, and crystallinity may be changed. The metal ions 20 to be adsorbed are not necessarily the same ions as the removed metal ions 20 and may be other metal ions. In addition, the cross-linked metal organic structure and organic cross-linked product thus produced have voids inside as well as the metal organic structure, and therefore adsorbents of specific molecules other than metal ions in gases and liquids. Can also be used.
　以下において実施例を参照して本発明をより具体的に説明するが、これらによって、本発明の範囲は限定して解釈されない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not construed as being limited thereto.
［実施例１］（１）有機配位子Ｎ３－ＴＰＤＣの合成 [Example 1] (1) Synthesis of organic ligand N 3 -TPDC
Figure JPOXMLDOC01-appb-C000003
 　三方コック、ジムロート冷却管、セプタムラバー付き３００ｍｌ二口丸底フラスコにヨウ素２９.０ｇ(１１０ｍｍｏｌ,０．８eq/ｐ-キシレン)、オルト過ヨウ素酸１０．０ｇ(４４ｍｍｏｌ,０．３ｅｑ/ｐ-キシレン)を入れ、脱気アルゴン置換した。そこにｐ-キシレン１５.０ｇ(１４０ｍｍｏｌ)、酢酸９４ｍｌ、四塩化炭素３０ｍｌ、３０％硫酸水溶液 １６．６ｍｌを入れ、８５℃で加熱還流を行った。１８時間後、メタノールを用いた再沈殿により目的の生産物を確認し、系を室温まで放冷した。過剰の蒸留水、メタノールを加え不要物をろ別し、得られた個体をメタノールで固液洗浄、減圧乾燥し桃白色固体を得た。
Figure JPOXMLDOC01-appb-C000003
 Three-way cock, Dimroth condenser, 300 ml two-necked round bottom flask with septum rubber, iodine 29.0 g (110 mmol, 0.8 eq / p-xylene), orthoperiodic acid 10.0 g (44 mmol, 0.3 eq / p-xylene) ) And purged with argon. 15.0 g (140 mmol) of p-xylene, 94 ml of acetic acid, 30 ml of carbon tetrachloride, and 16.6 ml of 30% sulfuric acid aqueous solution were added thereto, and the mixture was heated to reflux at 85 ° C. After 18 hours, the desired product was confirmed by reprecipitation with methanol, and the system was allowed to cool to room temperature. Excess distilled water and methanol were added and unnecessary substances were filtered off. The obtained solid was washed with methanol and dried under reduced pressure to obtain a peach-white solid.
Figure JPOXMLDOC01-appb-C000004
 　セプタムラバー、三方コック、ジムロート付き１００ｍｌ二口丸底フラスコに化合物Ｓ１を２．５ｇ(７．０ｍｍｏｌ)、フッ化セシウム６．４ｇ(４２ｍｍｏｌ,６ｅｑ/Ｓ１)を加え脱気窒素置換を行った。１,４－ジオキサン５０ｍｌ、蒸留水２０ｍｌを加え、窒素バブリングを１時間行った。その後、４-(４,４,５,５-テトラメチル-１,３,２-ジオキサボロラン-２-イル)安息香酸メチル４．０ｇ(１５ｍｍｏｌ,２．２ｅｑ/Ｓ1)、[１,１’-ビス(ジフェニルホスフィノ)フェロセン]ジクロロパラジウム(II) ジクロロメタン錯体０．５ｇ(０．０２５ｅｑ/Ｓ１)を加え、加熱還流を行った。6時間後、ＴＬＣ(シリカゲル、クロロホルム)による反応追跡を行い、原料の消失を確認後、反応を停止した。溶媒を減圧留去した残渣にトルエンを加え、飽和塩化ナトリウム水溶液にて洗浄後、無水硫酸ナトリウムで乾燥した。溶媒を減圧留去後、残渣をカラムクロマトグラフィー(シリカゲル、クロロホルム)により精製を行い、黄白色固体を得た。
Figure JPOXMLDOC01-appb-C000004
 2.5 g (7.0 mmol) of compound S1 and 6.4 g (42 mmol, 6 eq / S1) of compound S1 were added to a 100 ml two-necked round bottom flask equipped with a septa rubber, a three-way cock and a Jimroth to perform deaeration and nitrogen substitution. 50 ml of 1,4-dioxane and 20 ml of distilled water were added, and nitrogen bubbling was performed for 1 hour. Thereafter, 4.0 g (15 mmol, 2.2 eq / S1) of methyl 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate, [1,1′- Bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane complex 0.5 g (0.025 eq / S1) was added, and the mixture was heated to reflux. After 6 hours, the reaction was traced by TLC (silica gel, chloroform), and after confirming disappearance of the raw materials, the reaction was stopped. Toluene was added to the residue obtained by evaporating the solvent under reduced pressure, washed with a saturated aqueous sodium chloride solution, and then dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by column chromatography (silica gel, chloroform) to obtain a yellowish white solid.
Figure JPOXMLDOC01-appb-C000005
 　三方コック、ジムロート冷却管、セプタムラバー付き１００ｍｌ二口丸底フラスコに、化合物Ｓ２を２．０ｇ(５．３ｍｍｏｌ)、Ｎ-ブロモスクシンイミド２．０ｇ(１１ｍｍｏｌ, ２．１ｅｑ/Ｓ２)を入れ脱気窒素置換した。ベンゼン２５ｍｌを加え、１時間窒素バブリングを行った。その後、過酸化ベンゾイル０．１０ｇ(０．５ｍｍｏｌ,０．２ｅｑ/Ｓ２)を加え、加熱還流を行った。５時間後反応を停止し、溶媒を減圧留去後、残渣をカラムクロマトグラフィー(シリカゲル、クロロホルム)により精製を行い、黄白固体を得た。
Figure JPOXMLDOC01-appb-C000005
 Compound S2 (2.0 g, 5.3 mmol) and N-bromosuccinimide (2.0 mmol, 11 eq, 2.1 eq / S2) were placed in a 100 ml two-necked round bottom flask equipped with a three-way cock, Dimroth condenser, and septum rubber, and degassed. Replaced with nitrogen. 25 ml of benzene was added and nitrogen bubbling was performed for 1 hour. Thereafter, 0.10 g (0.5 mmol, 0.2 eq / S2) of benzoyl peroxide was added, and the mixture was heated to reflux. After 5 hours, the reaction was stopped, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, chloroform) to obtain a yellowish white solid.
Figure JPOXMLDOC01-appb-C000006
 　ジムロート付き２５ｍｌ二口丸底フラスコに化合物Ｓ３を０．５０ｇ(０．９４ｍｍｏｌ)を加え、脱気アルゴン置換を行った。脱水ＤＭＦ２０ｍｌ、アジ化ナトリウム０．１５ｇ(２．３ｍｍｏｌ,２．５ｅｑ/Ｓ３)を加え、６０℃にて加熱還流を４時間行った。その後、酢酸エチルにて希釈し、抽出操作(塩化ナトリウム水溶液２回、蒸留水１回)を行い、無水硫酸ナトリウムにて乾燥した。溶媒を減圧留去し、白色固体を得た。
Figure JPOXMLDOC01-appb-C000006
 0.50 g (0.94 mmol) of Compound S3 was added to a 25 ml two-necked round bottom flask equipped with a Dimroth, and purged with argon. 20 ml of dehydrated DMF and 0.15 g (2.3 mmol, 2.5 eq / S3) of sodium azide were added, and the mixture was heated to reflux at 60 ° C. for 4 hours. Then, it diluted with ethyl acetate, extraction operation (2 times of sodium chloride aqueous solution, 1 time of distilled water) was performed, and it dried with anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain a white solid.
Figure JPOXMLDOC01-appb-C000007
 　ジムロート付き５０ｍｌ二口丸底フラスコに化合物Ｓ４を０．４１ｇ(０．５３ｍｍｏｌ)、ＴＨＦ２０ｍｌ、飽和水酸化カリウム水溶液３ｍｌを加え、７５℃にて加熱還流を４時間行った。ＴＬＣ(シリカゲル、クロロホルム)にて、原料成分の消失を確認し、ＴＨＦを減圧留去した。１Ｎ塩酸を加え、生じた沈殿をろ別することで黄白色固体を得た。
Figure JPOXMLDOC01-appb-C000007
 0.41 g (0.53 mmol) of Compound S4, 20 ml of THF, and 3 ml of a saturated aqueous potassium hydroxide solution were added to a 50 ml two-necked round bottom flask equipped with a Dimroth, and the mixture was heated to reflux at 75 ° C. for 4 hours. The disappearance of the raw material components was confirmed by TLC (silica gel, chloroform), and THF was distilled off under reduced pressure. 1N hydrochloric acid was added, and the resulting precipitate was filtered to obtain a yellowish white solid.
（２）架橋剤Ｃ１～Ｃ３の合成 (2) Synthesis of crosslinking agents C1 to C3
Figure JPOXMLDOC01-appb-C000008
 　５０ｍｌ二口ナスフラスコに０℃の条件下でエチレングリコール１．１ｇ(１８ｍｍｏｌ)、乾燥ＤＭＦ２０ ｍｌ、水素化ナトリウム２．１ｇ(８９ｍｍｏｌ,４．９ｅｑ/エチレングリコール)を加え、１５分間攪拌した。プロパルギルブロミド６ｍｌ(５０ｍｍｏｌ,２．８ｅｑ/エチレングリコール)を加え、室温にて攪拌した。２４時間後反応を停止し、分液操作(ジエチルエーテル、蒸留水) を行った。有機相を無水硫酸マグネシウムにて乾燥し、溶媒を減圧留去した。残渣をカラムクロマトグラフィー(シリカゲル、ヘキサン ： 酢酸エチル = ８：２)により精製を行い、黄色液体を得た。
Figure JPOXMLDOC01-appb-C000008
 To a 50 ml two-necked eggplant flask, 1.1 g (18 mmol) of ethylene glycol, 20 ml of dry DMF, and 2.1 g (89 mmol, 4.9 eq / ethylene glycol) of sodium hydride were added at 0 ° C. and stirred for 15 minutes. 6 ml (50 mmol, 2.8 eq / ethylene glycol) of propargyl bromide was added and stirred at room temperature. After 24 hours, the reaction was stopped, and a liquid separation operation (diethyl ether, distilled water) was performed. The organic phase was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, hexane: ethyl acetate = 8: 2) to obtain a yellow liquid.
Figure JPOXMLDOC01-appb-C000009
 　１００ｍｌ二口ナスフラスコにフロログルシノール(脱水)を０．４３ｇ(３．３ｍｍｏｌ)、炭酸カリウム１．８ｇ(１３ｍｍｏｌ,１．５ｅｑ/－ＯＨ １unit)を加え、乾燥ＤＭＦ１０ｍｌを加え１．５時間５０℃にて加熱攪拌した。プロパルギルブロミド１．０ｍｌ(１３ｍｍｏｌ,１．５ｅｑ/－ＯＨ １unit)加え、６５℃にて加熱攪拌した。９．５時間後反応を停止し、分液操作(ジクロロメタン, 蒸留水) を行い、有機相を無水硫酸ナトリウムにて乾燥した。溶媒を減圧留去後、残渣をカラムクロマトグラフィー(シリカゲル、ジクロロメタン)にて精製を行い、黄白色固体を得た。
Figure JPOXMLDOC01-appb-C000009
 To a 100 ml two-necked eggplant flask, 0.43 g (3.3 mmol) of phloroglucinol (dehydrated) and 1.8 g (13 mmol, 1.5 eq / -OH 1 unit) of potassium carbonate were added, and 10 ml of dry DMF was added for 1.5 hours. The mixture was heated and stirred at ° C. Propargyl bromide 1.0 ml (13 mmol, 1.5 eq / -OH 1 unit) was added, and the mixture was heated and stirred at 65 ° C. After 9.5 hours, the reaction was stopped, liquid separation operation (dichloromethane, distilled water) was performed, and the organic phase was dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by column chromatography (silica gel, dichloromethane) to obtain a yellowish white solid.
Figure JPOXMLDOC01-appb-C000010
 　５０ｍｌ二口ナスフラスコにペンタエリトリトール１．５０ｇ(１１ｍｍｏｌ)、水素化ナトリウム２．１１ｇ(８８ｍｍｏｌ,８ｅｑ/Ｃ２)を入れ、脱気窒素置換した。乾燥ＤＭＦ２０ｍｌを加え０℃で３時間攪拌した。プロパルギルブロミド１０．０ｇ(８４ｍｍｏｌ,１２ｅｑ/Ｃ２)を加え、室温にて加熱攪拌した。２４時間後反応を停止し、分液操作(ジエチルエーテル、蒸留水) を行った。有機相を無水硫酸マグネシウムにて乾燥し、溶媒を減圧留去した。残渣をカラムクロマトグラフィー(シリカゲル、ヘキサン ： 酢酸エチル = ８：２)により精製を行い、黄色液体を得た。
Figure JPOXMLDOC01-appb-C000010
 A 50 ml two-necked eggplant flask was charged with 1.50 g (11 mmol) of pentaerythritol and 2.11 g (88 mmol, 8 eq / C2) of sodium hydride and purged with nitrogen. 20 ml of dry DMF was added and stirred at 0 ° C. for 3 hours. Propargyl bromide 10.0 g (84 mmol, 12 eq / C2) was added, and the mixture was heated and stirred at room temperature. After 24 hours, the reaction was stopped, and a liquid separation operation (diethyl ether, distilled water) was performed. The organic phase was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, hexane: ethyl acetate = 8: 2) to obtain a yellow liquid.
　金属有機構造体Ｎ３－ＭＯＦ－１５の合成
　サンプル管に、Ｎ３-ＴＰＤＣ２８ｍｇ、硝酸亜鉛六水和物５７ｍｇ、ＤＥＦ５ｍｌを加えて溶解させた。８０℃にて３日間、加熱静置して立方晶系の黄色結晶を得た。 Synthesis of Metal Organic Structure N 3 -MOF-15 To a sample tube, 28 mg of N 3 -TPDC, 57 mg of zinc nitrate hexahydrate and 5 ml of DEF were added and dissolved. The mixture was allowed to stand at 80 ° C. for 3 days to obtain cubic yellow crystals.
　架橋型金属有機構造体ＣＬ－ＭＯＦ－１５の合成
　スライドガラス上に、数粒の金属有機構造体Ｎ３－ＭＯＦ－１５を静置して、架橋剤Ｃ３のＮ,Ｎ-ジエチルホルムアミド溶液および触媒である塩化銅（Ｉ）のＮ,Ｎ-ジエチルホルムアミド溶液を滴下した（表１のサンプルＮｏ１および２）。また、バイアル管に、数粒の金属有機構造体Ｎ３－ＭＯＦ－１５を添加し、架橋剤Ｃ３および触媒である塩化銅（Ｉ）のＮ,Ｎ-ジエチルホルムアミド溶液を加えた（表１のサンプルＮｏ３～１０）。例えば、サンプルＮｏ９では、サンプル管に金属有機構造体Ｎ３－ＭＯＦ－１５ 約１０ｍｇ、架橋剤Ｃ３/ＤＥＦ溶液(０．１Ｍ)１ｍｌを加え、塩化銅（Ｉ）/ＤＥＦ溶液２０μｌ、８０℃にて７日間加熱静置して、立方晶系の黄色結晶を得た。 Synthesis of cross-linked metal organic structure CL-MOF-15 A few particles of metal organic structure N 3 -MOF-15 were allowed to stand on a slide glass, and an N, N-diethylformamide solution of a cross-linking agent C3 and a catalyst An N, N-diethylformamide solution of copper (I) chloride was dropped (samples No. 1 and 2 in Table 1). In addition, several particles of metal organic structure N 3 -MOF-15 were added to the vial tube, and a N, N-diethylformamide solution of copper (I) chloride as a cross-linking agent C3 and a catalyst was added (in Table 1). Sample No. 3-10). For example, in sample No. 9, about 10 mg of metal organic structure N 3 -MOF-15 and 1 ml of cross-linking agent C3 / DEF solution (0.1 M) are added to the sample tube, and 20 μl of copper (I) chloride / DEF solution at 80 ° C. For 7 days to obtain cubic yellow crystals.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　アジド基の消滅は、ＡＴＲ－ＩＲの測定において、２０９０ｃｍ－１のピークの消失によって確認した。図２には、金属有機構造体Ｎ３－ＭＯＦ－１５のＡＴＲ－ＩＲスペクトルと、表１のサンプルＮｏ５のＡＴＲ－ＩＲスペクトルとを示す。図２に示されるように、サンプルＮｏ５では、２０９０ｃｍ－１のピークが消失していることがわかる。 The disappearance of the azide group was confirmed by the disappearance of the 2090 cm −1 peak in the ATR-IR measurement. FIG. 2 shows an ATR-IR spectrum of the metal organic structure N 3 -MOF-15 and an ATR-IR spectrum of sample No. 5 in Table 1. As shown in FIG. 2, in sample No. 5, it can be seen that the peak at 2090 cm −1 has disappeared.
　図３には、金属有機構造体Ｎ３－ＭＯＦ－１５の光学顕微鏡写真と、表１のサンプルＮｏ５の光学顕微鏡写真とを示す。サンプルＮｏ５も、金属有機構造体Ｎ３－ＭＯＦ－１５と同様の立方晶形黄色結晶であることがわかる。 FIG. 3 shows an optical micrograph of the metal organic structure N 3 -MOF-15 and an optical micrograph of sample No. 5 in Table 1. Sample No. 5 is also a cubic yellow crystal similar to the metal organic structure N 3 -MOF-15.
　図４には、金属有機構造体Ｎ３－ＭＯＦ－１５のＸＲＰＤパターンと、表１のサンプルＮｏ５のＸＲＰＤパターンとを示す。いずれのＸＲＰＤパターンにおいても、ピークが一致していることから、結晶構造が維持されたまま架橋反応が進行したことがわかる。 FIG. 4 shows the XRPD pattern of the metal organic structure N 3 -MOF-15 and the XRPD pattern of sample No. 5 in Table 1. In any XRPD pattern, since the peaks are coincident, it can be understood that the crosslinking reaction has progressed while maintaining the crystal structure.
　有機物架橋体ＰＧ－ＭＯＦ－１５の合成
　表１のサンプルＮｏ５，Ｎｏ７およびＮｏ８の架橋型金属有機構造体ＣＬ－ＭＯＦ－１５を、プロトン化溶媒（３５％ＨＣｌ水溶液/ジエチルホルムアミド、１/７．５，ｖ/ｖ）に浸漬させた。浸漬により架橋型金属有機構造体ＣＬ－ＭＯＦ－１５が膨潤していく様子が確認された。図５Ａには、表１のサンプルＮｏ５の、浸漬前の光学顕微鏡写真（左側）と、浸漬後の光学顕微鏡写真（右側）が示される。図５Ａに示されるように、浸漬により膨潤して体積が約４．３４倍になっていることがわかる。図５Ｂには、表１のサンプルＮｏ７の、浸漬前の光学顕微鏡写真（左側）と、浸漬後の光学顕微鏡写真（右側）が示される。図５Ｂに示されるように、浸漬により膨潤して体積が約２．３７倍になっていることがわかる。 Synthesis of crosslinked organic substance PG-MOF-15 The crosslinked metal organic structures CL-MOF-15 of samples No. 5, No. 7 and No. 8 in Table 1 were converted into protonated solvents (35% HCl aqueous solution / diethylformamide, 1 / 7.5 , V / v). It was confirmed that the cross-linked metal organic structure CL-MOF-15 was swollen by the immersion. FIG. 5A shows an optical micrograph before immersion (left side) and an optical micrograph after immersion (right side) of sample No. 5 in Table 1. As shown in FIG. 5A, it can be seen that the volume is increased by about 4.34 times due to swelling by immersion. FIG. 5B shows an optical micrograph before immersion (left side) and an optical micrograph after immersion (right side) of sample No. 7 in Table 1. As shown in FIG. 5B, it can be seen that the volume is increased by about 2.37 times due to swelling by immersion.
　Ｎｏ５，Ｎｏ７およびＮｏ８の膨潤率を、下記表に示す。表２に示されるように、架橋反応させるときの架橋剤濃度が高いと、膨潤率が高くなることが示唆された（Ｎｏ５と、Ｎｏ７～８との比較）。架橋剤濃度が高すぎると、架橋剤によって金属構造体の配位子間を架橋できずに架橋率が低下するためであると考えられる。
Figure JPOXMLDOC01-appb-T000002
 The swelling ratios of No5, No7 and No8 are shown in the following table. As shown in Table 2, it was suggested that the higher the concentration of the crosslinking agent during the crosslinking reaction, the higher the swelling ratio (Comparison between No5 and No7 to No8). When the concentration of the crosslinking agent is too high, it is considered that the crosslinking rate is lowered because the ligands of the metal structure cannot be crosslinked by the crosslinking agent.
Figure JPOXMLDOC01-appb-T000002
　一方、架橋剤と反応させていない金属有機構造体Ｎ３－ＭＯＦ－１５を、同様にプロトン化溶媒（３５％ＨＣｌ水溶液/ジエチルホルムアミド、１/７．５，ｖ/ｖ）に浸漬させたところ、すぐに分解して構造を維持できなかった。よって、架橋型金属有機構造体ＣＬ－ＭＯＦ－１５では、架橋により配位子が固定されていることがわかる。 On the other hand, when the metal organic structure N 3 -MOF-15 not reacted with the crosslinking agent was similarly immersed in a protonated solvent (35% HCl aqueous solution / diethylformamide, 1 / 7.5, v / v) The structure could not be maintained by breaking down immediately. Therefore, it can be seen that in the crosslinked metal organic structure CL-MOF-15, the ligand is fixed by crosslinking.
　図６には、架橋剤と反応させていない金属有機構造体（参照サンプル；４,４'－ビフェニルジカルボン酸と亜鉛イオンからなる金属有機構造体）、架橋型金属有機構造体ＣＬ－ＭＯＦ－１５および有機物架橋体ＰＧ－ＭＯＦ－１５の、ＡＴＲ－ＩＲスペクトルを示す。有機物架橋体ＰＧ－ＭＯＦ－１５のスペクトルでは、金属有機構造体Ｎ３－ＭＯＦ－１５および架橋型金属有機構造体ＣＬ－ＭＯＦ－１５で観察された１３９０～１４００ｃｍ－１付近のピーク（Ｃ－Ｏ面変角）が、消失していることがわかる。そして、有機物架橋体ＰＧ－ＭＯＦ－１５のスペクトルにおけるカルボニル１６８０～１７００ｃｍ－１のピーク（Ｃ=Ｏ伸縮）は、金属有機構造体Ｎ３－ＭＯＦ－１５および架橋型金属有機構造体ＣＬ－ＭＯＦ－１５におけるピークからシフトしていることがわかる。 FIG. 6 shows a metal organic structure not reacted with a crosslinking agent (reference sample; metal organic structure composed of 4,4′-biphenyldicarboxylic acid and zinc ions), and a crosslinked metal organic structure CL-MOF-15. 2 shows an ATR-IR spectrum of the organic crosslinked product PG-MOF-15. In the spectrum of the organic crosslinked product PG-MOF-15, a peak around 1390 to 1400 cm −1 observed with the metal organic structure N 3 -MOF-15 and the crosslinked metal organic structure CL-MOF-15 (C—O It can be seen that (surface deflection) has disappeared. The peak of carbonyl 1680-1700 cm −1 (C═O stretching) in the spectrum of the organic crosslinked product PG-MOF-15 indicates the metal organic structure N 3 —MOF-15 and the crosslinked metal organic structure CL-MOF—. It can be seen that there is a shift from the peak at 15.
　これらのＡＴＲ－ＩＲスペクトルの観察結果から、有機物架橋体ＰＧ－ＭＯＦ－１５では亜鉛の配位結合が開裂しており、亜鉛が除去されていることがわかる。 From the observation results of these ATR-IR spectra, it can be seen that in the organic crosslinked product PG-MOF-15, the coordinate bond of zinc is cleaved and the zinc is removed.
　図７には、架橋剤と反応させていない金属有機構造体ＩＲ－ＭＯＦ－９（ビフェニル基を持つジカルボン酸をリンカーとし、亜鉛イオンを金属イオンとして合成した金属有機構造体である）、架橋型金属有機構造体ＣＬ－ＭＯＦ－１５および有機物架橋体ＰＧ－ＭＯＦ－１５の、ＸＰＳスペクトルを示す。ＸＰＳスペクトルの観察は、インジウム基板に試料をキャスト/乾燥させたものを測定基板とした。図７に示されるように、有機物架橋体ＰＧ－ＭＯＦ－１５のＸＰＳスペクトルでは、金属有機構造体ＩＲ－ＭＯＦ－９および架橋型金属有機構造体ＣＬ－ＭＯＦ－１５では観察された亜鉛のピーク（Ｚｎ　２Ｐ，１０００ｅＶ付近）が、消失していることがわかる。この結果からも、有機物架橋体ＰＧ－ＭＯＦ－１５では亜鉛が除去されていることがわかる。 FIG. 7 shows a metal organic structure IR-MOF-9 that is not reacted with a crosslinking agent (a metal organic structure synthesized by using a dicarboxylic acid having a biphenyl group as a linker and zinc ions as metal ions), a crosslinked type 2 shows XPS spectra of metal-organic structure CL-MOF-15 and organic crosslinked product PG-MOF-15. The XPS spectrum was observed by using a sample substrate cast / dried on an indium substrate as a measurement substrate. As shown in FIG. 7, in the XPS spectrum of the organic crosslinked product PG-MOF-15, the zinc peak observed in the metal organic structure IR-MOF-9 and the crosslinked metal organic structure CL-MOF-15 ( It can be seen that Zn 2P, around 1000 eV) has disappeared. This result also shows that zinc is removed from the organic crosslinked product PG-MOF-15.
　図８には、架橋剤と反応させていない金属有機構造体Ｎ３－ＭＯＦ－１５、架橋型金属有機構造体ＣＬ－ＭＯＦ－１５および有機物架橋体ＰＧ－ＭＯＦ－１５のゲスト（溶媒であるジエチルホルムアミドＤＥＦ）包接能を評価するための、熱重量分析（ＴＧＡ）試験の結果が示される。熱重量分析（ＴＧＡ）試験は、試料量約５ｍｇ，測定温度領域３０～５００℃，昇温速度３．０℃/分，窒素ガス流速２００ｍｌ/分の条件で行った。 FIG. 8 shows guests of the metal organic structure N 3 -MOF-15, the cross-linked metal organic structure CL-MOF-15, and the organic cross-linked product PG-MOF-15 that were not reacted with the cross-linking agent (diethyl as a solvent). The results of a thermogravimetric analysis (TGA) test to evaluate the inclusion ability of formamide DEF) are shown. The thermogravimetric analysis (TGA) test was performed under the conditions of a sample amount of about 5 mg, a measurement temperature region of 30 to 500 ° C., a temperature rising rate of 3.0 ° C./min, and a nitrogen gas flow rate of 200 ml / min.
　金属有機構造体Ｎ３－ＭＯＦ－１５の質量曲線では、３０℃から１５０℃にまで急激な１回目の質量減少が起こり；２００℃付近で２回目の質量減少が起こり；３８０℃から４５０℃にかけて３回目の質量減少が起こっている。１回目の質量減少は、ゲストである溶媒のジエチルホルムアミドが除去されることで生じているものと思われる。２回目の質量減少は、アジド基の分解によるものと思われる。３回目の質量減少は、構造の骨格自体が分解することによるものと思われる。 In the mass curve of the metal organic structure N 3 -MOF-15, the first mass decrease occurs rapidly from 30 ° C. to 150 ° C .; the second mass decrease occurs near 200 ° C .; from 380 ° C. to 450 ° C. A third mass loss has occurred. The first decrease in mass appears to be caused by the removal of the guest solvent diethylformamide. The second mass loss is believed to be due to the decomposition of the azido group. The third mass loss is believed to be due to the decomposition of the structural skeleton itself.
　架橋型金属有機構造体ＣＬ－ＭＯＦ－１５の質量曲線では、２回目の質量減少（２００℃付近）が見られない。架橋型金属有機構造体ＣＬ－ＭＯＦ－１５にはアジド基がないためであると考えられる。さらに、架橋型金属有機構造体ＣＬ－ＭＯＦ－１５の質量曲線での１回目の質量減少は、金属有機構造体Ｎ３－ＭＯＦ－１５の質量曲線での１回目の質量減少よりも少ない。このことは、架橋型金属有機構造体ＣＬ－ＭＯＦ－１５は、架橋により空孔の体積が減少しているためであると考えられる。 In the mass curve of the crosslinked metal organic structure CL-MOF-15, the second mass reduction (around 200 ° C.) is not observed. This is probably because the crosslinked metal organic structure CL-MOF-15 has no azide group. Further, the first mass decrease in the mass curve of the cross-linked metal organic structure CL-MOF-15 is less than the first mass decrease in the mass curve of the metal organic structure N 3 -MOF-15. This is presumably because the volume of pores in the cross-linked metal organic structure CL-MOF-15 is reduced by cross-linking.
　有機物架橋体ＰＧ－ＭＯＦ－１５の質量曲線では、１回目の質量減少が大きいことがわかる。このことは、配位結合が開裂したために、空孔の体積が高まり、ゲスト包接能が向上しているためであると考えられる。 In the mass curve of the organic crosslinked product PG-MOF-15, it is understood that the first mass reduction is large. This is probably because the coordination bond was cleaved, so that the volume of the vacancies increased and the guest inclusion ability was improved.
　有機物架橋体ＰＧ－ＭＯＦ－１５から架橋型金属有機構造体ＣＬ－ＭＯＦ－１５への再生
　金属イオン（亜鉛イオン）を除去した有機物架橋体ＰＧ－ＭＯＦ－１５に、亜鉛イオンを再配位させることで、架橋型金属有機構造体ＣＬ－ＭＯＦ－１５に再生させた。ここで再生された架橋型金属有機構造体をＲｅＣＬ－ＭＯＦ－１５と呼ぶ。 Regeneration from crosslinked organic material PG-MOF-15 to crosslinked metal organic structure CL-MOF-15 Re-coordination of zinc ions to crosslinked organic material PG-MOF-15 from which metal ions (zinc ions) have been removed Thus, it was regenerated into a cross-linked metal organic structure CL-MOF-15. The regenerated crosslinked organic metal structure is called ReCL-MOF-15.
　有機物架橋体ＰＧ－ＭＯＦ－１５を、表３に示す条件にて金属を再配位させた。具体的には、例えば下記表のＮｏ２では、有機物架橋体ＰＧ－ＭＯＦ－１５を０．２５ｍＭ　硝酸亜鉛六水和物/ＤＥＦ溶液に浸透させ、３６時間、８０℃にて静置した。
Figure JPOXMLDOC01-appb-T000003
 In the organic crosslinked product PG-MOF-15, the metal was re-coordinated under the conditions shown in Table 3. Specifically, for example, in No. 2 in the table below, the organic crosslinked product PG-MOF-15 was infiltrated into a 0.25 mM zinc nitrate hexahydrate / DEF solution and allowed to stand at 80 ° C. for 36 hours.
Figure JPOXMLDOC01-appb-T000003
　図９には、金属有機構造体Ｎ３－ＭＯＦ－１５、架橋型金属有機構造体ＣＬ－ＭＯＦ－１５、有機物架橋体ＰＧ－ＭＯＦ－１５および再生された架橋型金属有機構造体ＲｅＣＬ－ＭＯＦ－１５のＡＴＲ－ＩＲスペクトルを示す。 FIG. 9 shows metal organic structure N 3 -MOF-15, cross-linked metal organic structure CL-MOF-15, organic cross-linked body PG-MOF-15, and regenerated cross-linked metal organic structure ReCL-MOF- 15 ATR-IR spectra are shown.
　図９に示されるように、再生された架橋型金属有機構造体ＲｅＣＬ－ＭＯＦ－１５のＩＲスペクトルでは、有機物架橋体ＰＧ－ＭＯＦ－１５のＩＲスペクトルでは消失していた１３９０ｃｍ－１のピーク（Ｃ－Ｏ面変角）が、再び現れていることがわかる。また、再生された架橋型金属有機構造体ＲｅＣＬ－ＭＯＦ－１５のスペクトルにおけるカルボニル１６８０～１７００ｃｍ－１のピーク（Ｃ=Ｏ伸縮振動）は、有機物架橋体ＰＧ－ＭＯＦ－１５のピークからシフトしていることがわかる。これらのＡＴＲ－ＩＲスペクトルの観察結果から、再生された架橋型金属有機構造体ＲｅＣＬ－ＭＯＦ－１５には金属イオン（亜鉛イオン）が再配位していることがわかる。 As shown in FIG. 9, in the IR spectrum of the regenerated crosslinked metal-organic structure ReCL-MOF-15, the peak of 1390 cm −1 disappeared in the IR spectrum of the organic crosslinked product PG-MOF-15 (C It can be seen that -O-plane deflection) appears again. In addition, the peak of carbonyl 1680-1700 cm −1 (C═O stretching vibration) in the spectrum of the regenerated crosslinked metal organic structure ReCL-MOF-15 is shifted from the peak of the organic crosslinked product PG-MOF-15. I understand that. From the observation results of these ATR-IR spectra, it can be seen that metal ions (zinc ions) are re-coordinated to the regenerated crosslinked metal organic structure ReCL-MOF-15.
（実施例２）
　金属有機構造体ＣＤ－ＭＯＦ（[(C48H80O40)(KOH)2]n.）の合成
　以下の構造式で示されるγ－シクロデキストリン（γ－ＣＤ）を最小の構成単位とし、γ－ＣＤの水酸基とカリウムイオンの配位結合によりγ－ＣＤが３次元的に規則正しく会合した構造を持つ、ＣＤ－ＭＯＦを合成した。ＣＤ－ＭＯＦの組成式は、[(C48H80O40)(KOH)2]nで表される。具体的には、Angew. Chem. Int. Ed. 2010, 49, 8630.に記載の方法に従って合成した。
Figure JPOXMLDOC01-appb-C000011
 (Example 2)
Synthesis of metal organic structure CD-MOF ([(C 48 H 80 O 40 ) (KOH) 2 ] n.) Γ-cyclodextrin (γ-CD) represented by the following structural formula is the smallest structural unit, A CD-MOF having a structure in which γ-CD is regularly and three-dimensionally associated by a coordinate bond between a hydroxyl group of γ-CD and a potassium ion was synthesized. The composition formula of CD-MOF is represented by [(C 48 H 80 O 40 ) (KOH) 2 ] n. Specifically, it was synthesized according to the method described in Angew. Chem. Int. Ed. 2010, 49, 8630.
Figure JPOXMLDOC01-appb-C000011
　６分子のγ－ＣＤが会合したＣＤ－ＭＯＦ（（γ－ＣＤ）６と称する）のボールアンドスティックモデルを図１４に、複数の（γ－ＣＤ）６が体心立方格子構造で会合したＣＤ－ＭＯＦの空間充填モデルを図１５示す。 FIG. 14 shows a ball-and-stick model of CD-MOF (referred to as (γ-CD) 6) in which six molecules of γ-CD are associated, and CD in which a plurality of (γ-CD) 6 are associated in a body-centered cubic lattice structure A space filling model of -MOF is shown in FIG.
　架橋型金属有機構造体ＣＬ－ＣＤ－ＭＯＦの合成サンプル菅に金属有機構造体ＣＤ－ＭＯＦを２０ｍｇ取り、１．５～５．０Ｍの濃度でエチレングリコールジグリシジルエーテル（架橋剤Ｌ１）／エタノール溶液を加え、６５℃で３日間加熱静置させ内部架橋反応を行ない、透明結晶として架橋型金属有機構造体ＣＬ－ＣＤ－ＭＯＦを得た。 20 mg of metal organic structure CD-MOF is taken in a sample of the synthesis of cross-linked metal organic structure CL-CD-MOF, and ethylene glycol diglycidyl ether (crosslinking agent L1) / ethanol solution at a concentration of 1.5 to 5.0 M And allowed to stand at 65 ° C. for 3 days to carry out an internal crosslinking reaction to obtain a crosslinked metal organic structure CL-CD-MOF as transparent crystals.
有機物架橋体ＰＧ－ＣＤ－ＭＯＦの合成スライドガラス上に取り出した架橋型金属有機構造体ＣＬ－ＣＤ－ＭＯＦを水とエタノールの混合溶媒（１：１）、水の順に浸漬させ、加水分解により、カリウムイオンの配位を除去することでアモルファス状の物質を得た。図１０には、架橋型金属有機構造体ＣＬ－ＣＤ－ＭＯＦが溶媒中で有機物架橋体ＰＧ－ＣＤ－ＭＯＦに変化する様子を光学顕微鏡で観察したものを示す。形状は変化せず、膨潤によりサイズのみが変化した。 Synthesis of organic crosslinked product PG-CD-MOF The crosslinked metal organic structure CL-CD-MOF taken out on the slide glass was immersed in a mixed solvent of water and ethanol (1: 1) in order of water, and then hydrolyzed. An amorphous substance was obtained by removing the coordination of potassium ions. FIG. 10 shows a state in which the cross-linked metal organic structure CL-CD-MOF is changed to the organic cross-linked product PG-CD-MOF in a solvent, as observed with an optical microscope. The shape did not change, only the size changed due to swelling.
　図１１では架橋剤Ｌ１のさまざまな濃度領域で内部架橋反応を行い、カリウムイオンの配位を除去することで得られた有機物架橋体ＰＧ－ＣＤ－ＭＯＦの膨潤度を示す。膨潤度ＱはＱ＝（ＬＰＧ－ＣＤ－ＭＯＦ／ＬＣＬ－ＣＤ－ＭＯＦ）３で計算した。ここでＬＰＧ－ＣＤ－ＭＯＦは有機物架橋体ＰＧ－ＣＤ－ＭＯＦの結晶の一辺の長さ、ＬＣＬ－ＣＤ－ＭＯＦは架橋型金属有機構造体ＣＬ－ＣＤ－ＭＯＦの一辺の長さを表す。架橋剤Ｌ１の濃度が１．５～２．０Ｍ の場合で最も膨潤度が低く、架橋反応が最も高密度で進行していることを示している。以降、架橋剤Ｌ１の濃度は１．５Ｍで統一して実験を行なった。 FIG. 11 shows the degree of swelling of the organic crosslinked product PG-CD-MOF obtained by carrying out an internal crosslinking reaction in various concentration regions of the crosslinking agent L1 and removing the coordination of potassium ions. The degree of swelling Q was calculated by Q = ( LPG-CD-MOF / LCL-CD-MOF ) 3 . Here, L PG-CD-MOF represents the length of one side of the crystal of the organic crosslinked product PG-CD-MOF, and L CL-CD-MOF represents the length of one side of the crosslinked metal-organic structure CL-CD-MOF. . When the concentration of the crosslinking agent L1 is 1.5 to 2.0M, the degree of swelling is the lowest, indicating that the crosslinking reaction proceeds at the highest density. Thereafter, the experiment was conducted with the concentration of the cross-linking agent L1 unified at 1.5M.
　架橋剤Ｌ１により生成する架橋型金属有機構造体ＣＬ－ＣＤ－ＭＯＦのＦＴ－ＩＲスペクトルを測定した結果が図１２に示される。γ－ＣＤに由来するＣ－Ｏ－Ｃの伸縮振動（１１５０－１１２０ｃｍ－１）がブロードしていること、及び架橋剤Ｌ１を修飾したことによるメチレン鎖由来のピーク強度（２９２０－２８５０ｃｍ－１）が増加していることが確認された。このことから、架橋剤Ｌ１が予想通りに反応していると考えられる。 FIG. 12 shows the result of measuring the FT-IR spectrum of the cross-linked metal organic structure CL-CD-MOF produced by the cross-linking agent L1. The stretching intensity of C—O—C derived from γ-CD (1150-1120 cm-1) is broad, and the peak intensity derived from the methylene chain due to modification of the crosslinking agent L1 (2920-2850 cm-1) Was confirmed to increase. From this, it is thought that the crosslinking agent L1 is reacting as expected.
　形態観察
　作製した金属有機構造体ＣＤ－ＭＯＦおよび架橋型金属有機構造体ＣＬ－ＣＤ－ＭＯＦ、有機物架橋体ＰＧ－ＣＤ－ＭＯＦの形態を評価するため、走査型電子顕微鏡（ＳＥＭ）観察を行なった。本実験で用いたサンプルは、２４時間メタノールで蒸気拡散させ作製した金属有機構造体ＣＤ－ＭＯＦ、１．５Mの架橋剤Ｌ１溶液で内部架橋した架橋型金属有機構造体ＣＬ－ＣＤ－ＭＯＦ、それに水を添加しカリウムイオンの配位を除去して作製した有機物架橋体ＰＧ－ＣＤ－ＭＯＦである。測定は８０℃で一晩放置し、その後１２時間真空乾燥したサンプルをカーボンテープに乗せ、白金蒸着して行なった。 Morphological observation In order to evaluate the morphology of the prepared metal organic structure CD-MOF, crosslinked metal organic structure CL-CD-MOF, and organic crosslinked substance PG-CD-MOF, scanning electron microscope (SEM) observation was performed. . Samples used in this experiment were a metal organic structure CD-MOF prepared by vapor diffusion with methanol for 24 hours, a cross-linked metal organic structure CL-CD-MOF internally cross-linked with a 1.5M cross-linking agent L1 solution, This is an organic crosslinked product PG-CD-MOF prepared by adding water to remove coordination of potassium ions. The measurement was carried out overnight at 80 ° C., and then a vacuum-dried sample for 12 hours was placed on a carbon tape and deposited with platinum.
　ＳＥＭ観察の結果、図１３に示す通り、いずれも立方体形状の物体であった。結晶である金属有機構造体ＣＤ－ＭＯＦは立方体の形状をしており、架橋反応の生成物である架橋型金属有機構造体ＣＬ－ＣＤ－ＭＯＦや加水分解後の有機物架橋体ＰＧ－ＣＤ－ＭＯＦのどちらも金属有機構造体ＣＤ－ＭＯＦの形態を維持していることがわかった。また溶媒で膨潤したサンプルだけでなく、乾燥したサンプルにおいても有機物架橋体ＰＧ－ＣＤ－ＭＯＦが原料である結晶由来の直線的な辺と頂点をもつ構造体であった。 As a result of SEM observation, as shown in FIG. 13, all were cubic objects. The metal organic structure CD-MOF which is a crystal has a cubic shape, and the crosslinked metal organic structure CL-CD-MOF which is a product of the crosslinking reaction and the organic compound crosslinked body PG-CD-MOF after hydrolysis. Both of them were found to maintain the form of the metal organic structure CD-MOF. In addition to the sample swollen with the solvent, the dried sample also had a structure with linear sides and vertices derived from the crystals from which the organic crosslinked product PG-CD-MOF was derived.
　本発明により、共有結合性有機構造体の新しい設計方針が提供され、これまでにない構造を有する共有結合性の有機構造体の提供が可能となる。さらには、本発明により提供される有機物架橋体は、金属イオン吸着能を有するので、金属イオンなどの金属回収原料への応用や、薬剤の徐放システムなどへの応用も可能である。 According to the present invention, a new design policy of a covalently bonded organic structure is provided, and a covalently bonded organic structure having an unprecedented structure can be provided. Furthermore, since the organic cross-linked product provided by the present invention has a metal ion adsorption ability, it can be applied to a metal recovery raw material such as metal ions or a sustained release system of a drug.
　１０　有機配位子
　１１　官能基
　２０　金属イオン
　３０　金属有機構造体
　４０　架橋剤
　５０　架橋型金属有機構造体
　６０　有機物架橋体
  DESCRIPTION OF SYMBOLS 10 Organic ligand 11 Functional group 20 Metal ion 30 Metal organic structure 40 Crosslinking agent 50 Crosslinking type metal organic structure 60 Organic substance crosslinked body

Claims (6)

  1. 　有機配位子と、前記有機配位子を連結する金属イオンを含む金属有機構造体を用意するステップＡと、
    　前記配位子を架橋剤で架橋して架橋型金属有機構造体とするステップＢと、
    　を有する、架橋型金属有機構造体の製造方法。     Preparing a metal organic structure containing an organic ligand and a metal ion linking the organic ligand; and
    Step B in which the ligand is crosslinked with a crosslinking agent to form a crosslinked metal organic structure,
    The manufacturing method of a bridge | crosslinking type metal organic structure which has these.
  2. 　前記有機配位子は官能基を有し、かつ前記架橋剤は、前記官能基と反応して共有結合を形成できる２以上の官能基を有する、請求項１に記載の架橋型金属有機構造体の製造方法。 The cross-linked metal organic structure according to claim 1, wherein the organic ligand has a functional group, and the cross-linking agent has two or more functional groups capable of reacting with the functional group to form a covalent bond. Manufacturing method.
  3. 　有機配位子と、前記有機配位子を連結する金属イオンを含む金属有機構造体を用意するステップＡと、
    　前記配位子を架橋剤で架橋して架橋型金属有機構造体とするステップＢと、
    　前記架橋型金属有機構造体から、前記金属イオンのうちの一部または全部を除去するステップＣと、
    　を有する、有機物架橋体を製造する方法。     Preparing a metal organic structure containing an organic ligand and a metal ion linking the organic ligand; and
    Step B in which the ligand is crosslinked with a crosslinking agent to form a crosslinked metal organic structure,
    Removing some or all of the metal ions from the cross-linked metal organic structure; and
    A method for producing a crosslinked organic material, comprising:
  4. 　有機配位子と、前記有機配位子を連結する金属イオンと、前記有機配位子を架橋する架橋基とを含む、架橋型金属有機構造体。 A crosslinked metal organic structure comprising an organic ligand, a metal ion that links the organic ligand, and a crosslinking group that bridges the organic ligand.
  5. 　請求項４に記載の架橋型金属有機構造体から、前記金属イオンのうちの一部または全部を除去して得られる、有機物架橋体。 5. A crosslinked organic substance obtained by removing a part or all of the metal ions from the crosslinked metal-organic structure according to claim 4.
  6. 　前記有機物架橋体は、金属イオンを吸着することで前記架橋型金属有機構造体となることができる、請求項５に記載の有機物架橋体。
          The said organic bridge | crosslinking body is an organic substance bridge | crosslinking body of Claim 5 which can become the said bridge | crosslinking type metal organic structure by adsorbing a metal ion.
PCT/JP2012/001659 2011-03-09 2012-03-09 Crosslinked metallic organic structure and crosslinked organic material, and processes for producing same WO2012120905A1 (en)

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