WO2023033035A1 - 二酸化炭素捕捉剤、金属有機構造体、及び化合物 - Google Patents

二酸化炭素捕捉剤、金属有機構造体、及び化合物 Download PDF

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WO2023033035A1
WO2023033035A1 PCT/JP2022/032745 JP2022032745W WO2023033035A1 WO 2023033035 A1 WO2023033035 A1 WO 2023033035A1 JP 2022032745 W JP2022032745 W JP 2022032745W WO 2023033035 A1 WO2023033035 A1 WO 2023033035A1
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halogen atom
optionally substituted
group optionally
metal
carbon dioxide
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French (fr)
Japanese (ja)
Inventor
隆也 松本
正規 河野
博義 大津
パベル ユーソフ
雄貴 和田
光将 嶋田
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Tokyo Institute of Technology NUC
Eneos Corp
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Tokyo Institute of Technology NUC
Eneos Corp
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Priority to US18/687,587 priority Critical patent/US20240351002A1/en
Priority to JP2023545636A priority patent/JPWO2023033035A1/ja
Priority to CN202280058489.0A priority patent/CN117897225A/zh
Priority to EP22864617.0A priority patent/EP4397405A4/en
Publication of WO2023033035A1 publication Critical patent/WO2023033035A1/ja
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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 Table
    • C07F1/08—Copper compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/306—Surface area, e.g. BET-specific surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to a carbon dioxide scavenger, a metal organic framework that can be used for the carbon dioxide scavenger, and a compound that can be used as a ligand for the metal organic framework.
  • PCNs Porous network complexes
  • a gate-open MOF is also known as a metal organic framework (MOF) capable of trapping gas.
  • MOF metal organic framework
  • the open gate MOF has a larger volume after gas is trapped than before gas is trapped. That is, the gate-open MOF undergoes a structural change such as volumetric expansion by trapping gas (see, for example, Non-Patent Document 3). If the structural change of the MOF is large, the low durability of the MOF itself is regarded as a problem. Further, when the volume expansion of the MOF is large, the low durability of the MOF formed into a molded product is considered a problem.
  • the present invention provides a novel carbon dioxide scavenger capable of capturing carbon dioxide, a metal-organic framework that can be used as the carbon dioxide scavenger, and a compound that can be used as a ligand of the metal-organic framework. With the goal.
  • a carbon dioxide scavenger containing a metal organic structure, the metal-organic framework is capable of capturing carbon dioxide and desorbing carbon dioxide;
  • An isolated space is formed inside the metal-organic structure by the three-dimensional structure of the metal-organic structure, The isolated space is a space that can capture carbon dioxide and does not normally have a channel through which carbon dioxide can pass, Although the three-dimensional structure of the metal organic framework changes in the process of capturing carbon dioxide in the isolated space and in the process of desorbing carbon dioxide from the isolated space, carbon dioxide is captured in the isolated space.
  • the three-dimensional structure of the metal-organic structure when carbon dioxide is not trapped in the isolated space is the same as the three-dimensional structure of the metal-organic structure when carbon dioxide is not trapped in the isolated space; Carbon dioxide scavenger.
  • X 21 and X 23 are N and X 22 , X 24 and X 25 are CR, or X 22 and X 24 are N and X 21 , X 23 and X 25 are CR; Or, X 21 and X 25 are N and X 22 , X 23 and X 24 are CR.
  • X 31 and X 33 are N and X 32 , X 34 and X 35 are CR, or X 32 and X 34 are N and X 31 , X 33 and X 35 are CR; Or, X 31 and X 35 are N and X 32 , X 33 and X 34 are CR.
  • X 41 and X 43 are N and X 42 , X 44 and X 45 are CR, or X 42 and X 44 are N and X 41 , X 43 and X 45 are CR; Or, X 41 and X 45 are N and X 42 , X 43 and X 44 are CR.
  • Each R is independently a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl group is a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom).
  • R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl The group is optionally substituted with a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom.
  • Each R is independently a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl group is a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom).
  • R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl The group is optionally substituted with a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom.
  • X 11 and X 13 are N and X 12 , X 14 and X 15 are CR, or X 12 and X 14 are N and X 11 , X 13 and X 15 are CR; Or, X 11 and X 15 are N and X 12 , X 13 and X 14 are CR.
  • X 21 and X 23 are N and X 22 , X 24 and X 25 are CR, or X 22 and X 24 are N and X 21 , X 23 and X 25 are CR; Or, X 21 and X 25 are N and X 22 , X 23 and X 24 are CR.
  • X 31 and X 33 are N and X 32 , X 34 and X 35 are CR, or X 32 and X 34 are N and X 31 , X 33 and X 35 are CR; Or, X 31 and X 35 are N and X 32 , X 33 and X 34 are CR.
  • X 41 and X 43 are N and X 42 , X 44 and X 45 are CR, or X 42 and X 44 are N and X 41 , X 43 and X 45 are CR; Or, X 41 and X 45 are N and X 42 , X 43 and X 44 are CR.
  • Each R is independently a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl group is a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom).
  • R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl The group is optionally substituted with a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom.
  • Each R is independently a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl group is a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom).
  • R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl The group is optionally substituted with a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom. ) [13] The metal-organic framework according to [11] or [12], containing a halogen element as a constituent element.
  • the metal-organic framework according to any one of [11] to [13], wherein the composition formula is Cu 4 I 4 L, where L is the ligand.
  • the constituent element contains copper, The metal organic according to any one of [11] to [14], wherein the ligand is coordinated to the copper by one of the two nitrogen atoms of the pyrimidine ring of the ligand. Structure.
  • the constituent elements contain copper and iodine, The metal-organic structure according to any one of [11] to [15], wherein Cu 4 I 4 is present in the metal-organic structure in Cuban type.
  • the constituent elements contain copper and iodine, Cu 4 I 4 is present in the cubane type in the metal organic framework,
  • the composition formula is represented by Cu 4 I 4 L
  • the metal organic according to any one of [11] to [16], wherein the ligand is coordinated to the copper by one of the two nitrogen atoms of the pyrimidine ring of the ligand.
  • Structure [18] A carbon dioxide scavenger containing the metal organic framework according to any one of [11] to [17].
  • X 11 and X 13 are N and X 12 , X 14 and X 15 are CR, or X 12 and X 14 are N and X 11 , X 13 and X 15 are CR; Or, X 11 and X 15 are N and X 12 , X 13 and X 14 are CR.
  • X 21 and X 23 are N and X 22 , X 24 and X 25 are CR, or X 22 and X 24 are N and X 21 , X 23 and X 25 are CR; Or, X 21 and X 25 are N and X 22 , X 23 and X 24 are CR.
  • X 31 and X 33 are N and X 32 , X 34 and X 35 are CR, or X 32 and X 34 are N and X 31 , X 33 and X 35 are CR; Or, X 31 and X 35 are N and X 32 , X 33 and X 34 are CR.
  • X 41 and X 43 are N and X 42 , X 44 and X 45 are CR, or X 42 and X 44 are N and X 41 , X 43 and X 45 are CR; Or, X 41 and X 45 are N and X 42 , X 43 and X 44 are CR.
  • Each R is independently a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl group is a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom).
  • R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl The group is optionally substituted with a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom.
  • [20] The compound according to [19], which is a compound represented by the following formula (1-1).
  • Each R is independently a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl group is a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom).
  • R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl The group is optionally substituted with a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom. )
  • a new carbon dioxide scavenger capable of capturing carbon dioxide, a metal-organic framework that can be used as the carbon dioxide scavenger, and a compound that can be used as a ligand of the metal-organic framework are provided. can do.
  • FIG. 2 is a schematic diagram of an interpenetrating structure in which two frameworks interpenetrate.
  • . 1 is a schematic diagram of a Cuban-type structure;
  • FIG. 2 is a schematic diagram of the three-dimensional structure of an example of the metal-organic framework of the present invention (without carbon dioxide capture).
  • 1 is a schematic diagram of a three-dimensional structure (with carbon dioxide capture) of an example of the metal-organic framework of the present invention.
  • FIG. It is a single-crystal X-ray structural analysis result of a pyrimidine ligand (Lp) (No. 1). It is a single-crystal X-ray structural analysis result of a pyrimidine ligand (Lp) (Part 2).
  • FIG. 4 shows FT-IR measurement results of a metal organic framework [Cu 4 I 4 Lp] and a pyrimidine ligand (Lp) before solvent removal.
  • 1 is a diagram showing a single crystal structure of a metal organic framework [Cu 4 I 4 Lp] before solvent removal (No. 1);
  • FIG. 2 shows a single crystal structure of a metal-organic framework [Cu 4 I 4 Lp] before solvent removal (No. 2).
  • FIG. 10 is another view showing the single crystal structure of the metal organic framework [Cu 4 I 4 Lp] before solvent removal (No. 1).
  • FIG. 2 is another view showing the single crystal structure of the metal organic framework [Cu 4 I 4 Lp] before solvent removal (No. 2).
  • FIG. 3 is another view showing the single crystal structure of the metal organic framework [Cu 4 I 4 Lp] before solvent removal (No. 3).
  • FIG. 10 is still another diagram showing the single crystal structure of the metal-organic framework [Cu 4 I 4 Lp] before solvent removal (No. 1).
  • FIG. 11 is still another diagram showing the single crystal structure of the metal-organic framework [Cu 4 I 4 Lp] before solvent removal (No. 2). It is a PXRD measurement result of the metal-organic framework [Cu 4 I 4 Lp] before solvent removal.
  • Fig . 3 is an adsorption isotherm of a metal-organic framework [ Cu4I4Lp ].
  • FIG. 2 shows a single crystal structure of a metal-organic framework [Cu 4 I 4 Lp] after solvent removal;
  • FIG. 10 shows a single crystal structure of a metal-organic framework [Cu 4 I 4 Lp] after solvent removal;
  • FIG. 10 shows a single crystal structure of a metal-organic framework [Cu 4 I 4 L
  • the carbon dioxide scavenger of the present invention contains a metal organic framework.
  • the carbon dioxide scavenger may be the metal-organic framework itself.
  • the metal-organic framework is capable of trapping carbon dioxide and desorbing carbon dioxide.
  • An isolated space is formed inside the metal-organic framework due to the three-dimensional structure of the metal-organic framework.
  • An isolated space is a space that can trap carbon dioxide and normally does not have channels through which carbon dioxide can pass.
  • the three-dimensional structure of the metal-organic framework changes in the process in which carbon dioxide is trapped in the isolated space and in the process in which carbon dioxide is desorbed from the isolated space, but carbon dioxide leaves the isolated space.
  • the three-dimensional structure of the metal-organic framework when trapped is the same as the three-dimensional structure of the metal-organic framework when carbon dioxide is not trapped in the isolated space.
  • the normal state refers to the state of being placed in air at normal temperature (25°C) and normal pressure (1 atm).
  • a channel refers to a passageway between a space and another space or the outside through which carbon dioxide can pass. Whether a passage between a space and another space or the outside is passable for a molecule depends on the Kinetic Diameter of the molecule and the spatial size of the passage in terms of passability of the molecule. can judge.
  • the spatial size of the passage from the viewpoint of the passage possibility of molecules can be obtained from the position of the atoms forming the passage and the van der Waals radius of the atoms forming the passage.
  • a space narrowed by van der Waals radius from the position of each atom (referred to as a passing space) from the space surrounded by the atoms forming the passage becomes the passage.
  • a sphere with a diameter corresponding to the Kinetic Diameter of a molecule can pass through the passage space, the molecule will be able to pass through the passageway. It should be noted that the Kinetic If a sphere with a diameter corresponding to Diameter (2.57 ⁇ ) cannot pass through the passage space, no molecule can pass through that passage.
  • the positions of the atoms forming the passage can be determined by single crystal X-ray structure analysis.
  • Metal-organic frameworks are also known as Porous Coordination Polymers (PCPs).
  • a metal-organic framework has a framework.
  • a framework is constructed by binding a ligand to a metal or metal compound that serves as a node through a coordinate bond, and is composed of constituent elements and chemical bonds (mainly covalent and coordinate bonds). be done.
  • the present inventors have found that although the three-dimensional structure of the metal-organic framework changes in the process in which carbon dioxide is trapped in the isolated space and in the process in which carbon dioxide is desorbed from the isolated space, carbon dioxide is trapped in the isolated space.
  • a new metal-organic framework has been found that has the same three-dimensional structure as the metal-organic framework when carbon dioxide is trapped in an isolated space.
  • the new metal-organic framework discovered by the present inventors changes its three-dimensional structure in the process in which carbon dioxide is trapped in the isolated space and in the process in which carbon dioxide is desorbed from the isolated space.
  • the three-dimensional structure of the metal-organic framework when carbon dioxide is trapped in the isolated space and the three-dimensional structure of the metal-organic framework when carbon dioxide is not trapped in the isolated space are the same (hereinafter , such behavior in the metal-organic framework is sometimes referred to as "no conformational change before and after capturing carbon dioxide"). Therefore, the above-mentioned problem in the gate open type MOF is less likely to occur. This point is very useful in using the metal-organic framework.
  • the three-dimensional structure of the metal-organic framework when carbon dioxide is trapped in the isolated space is the same as the three-dimensional structure of the metal-organic framework when carbon dioxide is not trapped in the isolated space.
  • the lattice constants a 1 [ ⁇ ], b 1 [ ⁇ ], c 1 [ ⁇ ], ⁇ 1 [° ], ⁇ 1 [°], ⁇ 1 [°]
  • the lattice constants a 2 [ ⁇ ], b 2 [ ⁇ ] of the crystal structure of the metal-organic framework when carbon dioxide is not trapped in an isolated space.
  • c 2 [ ⁇ ], ⁇ 2 [°], ⁇ 2 [°], ⁇ 2 [°]) are within ⁇ 10%.
  • This rate of change is preferably within ⁇ 5%, more preferably within ⁇ 3%, and particularly preferably within ⁇ 1%.
  • FIG. 1 A schematic diagram of the interpenetrating structure is shown in FIG.
  • a first framework F1 and a second framework F2 interpenetrate.
  • the metal-organic framework forms such a structure (an interpenetrating structure in which two frameworks interpenetrate each other), and a change in the relative position of the two frameworks causes a moderate conformational change.
  • the present inventors consider that the elastic flexibility of the ligand is important as a feature of the metal organic framework, which does not undergo a conformational change before and after capturing carbon dioxide.
  • the structure of the ligand is not rigid, and there are some parts (bonds) in the skeleton of the ligand that cannot rotate but can twist (one part of the molecule changes its angle with respect to the rest). gives elastic flexibility to the ligand.
  • Ligand flexibility leads to conformational changes in the metal-organic framework. Since the flexibility is elastic, it is thought that the metal-organic framework can return to a stable structure when a factor (for example, pressure) that causes a change in the three-dimensional structure is removed.
  • the torsion originating from this carbon-carbon bond causes hydrogen atoms or substituents and aromatic hydrocarbon rings bound to nitrogen-containing aromatic heterocycles to be twisted when a factor (e.g., pressure) that causes a change in steric structure is removed. It is elastic because it reverts to reduce the physical proximity of the bonding hydrogens or substituents.
  • the aromatic hydrocarbon ring and the nitrogen-containing aromatic heterocyclic ring are bonded by a carbon-carbon bond, the state in which they are on the same plane is the highest energy state, that is, the most unfavorable state. If bulky substituents are present, the energy barrier can no longer be crossed and rotation is inhibited.
  • the angle formed by these planes varies depending on the presence or absence of substituents, the type of substituents, and the like.
  • the angle between the plane of the pyrimidine ring and the plane of the methyl-substituted benzene ring is about 70°. be.
  • the BET specific surface area of the metal-organic framework in the specific surface area measurement using N 2 is, for example, 1 m 2 /g or less.
  • a BET specific surface area of 1 m2 /g or less in specific surface area measurement using N2 means that the pores are isolated spaces.
  • the BET specific surface area can be determined by measuring the adsorption isotherm using N2 .
  • the adsorption isotherm can be measured using a gas adsorption measurement device (eg Microtrac Bell's fully automatic gas adsorption measurement device BELSORP MAX). Details of the measurement method are described in Examples.
  • the elements forming the isolated spaces and the carbon dioxide trapped in the isolated spaces do not form chemical bonds.
  • Chemical bonds here are covalent bonds, ionic bonds and hydrogen bonds. Whether or not the element forming the isolated space and the carbon dioxide trapped in the isolated space form a chemical bond can be determined from the type of element forming the isolated space and the size of the isolated space. can be done. The size of the isolated space can be obtained by calculating the result of single crystal X-ray structure analysis using Mercury software of CCDC (Cambridge Crystallographic Data Center).
  • the metal organic framework contains, for example, at least one of group II to XIV elements as constituent elements.
  • the group II to XIV elements are preferably Zr, Cd, Ti, Cu, Zn, Fe, Cr, Ni, Co, Mo, Hf, Mg, Al and Si, more preferably Cu and Zr. , Zn, and Cd.
  • the metal organic framework may contain, for example, a halogen element as a constituent element. Halogen elements include fluorine, chlorine, bromine and iodine.
  • the constituent element here is not an element that constitutes a ligand.
  • the metal-organic framework contains, for example, a compound having a nitrogen-containing aromatic heterocycle as a ligand. Examples of the nitrogen-containing aromatic heterocyclic ring include pyridine ring and pyrimidine ring.
  • the composition formula of the metal organic framework is preferably represented by Cu 4 I 4 L, where L is the ligand.
  • the compound having a nitrogen-containing aromatic heterocycle is preferably a compound represented by Formula (1) described below.
  • the compound represented by formula (1) may be defined by the proviso described later, and X 11 to X 15 , X 21 to X 25 , X 31 to X 35 and X 41 to X 45 are , one of X 11 to X 15 is N and the others are CR, one of X 21 to X 25 is N and the others are CR, one of X 31 to X 35 is N and the others are CR and one of X 41 to X 45 is N and the others are CR.
  • X 11 to X 15 , X 21 to X 25 , X 31 to X 35 and X 41 to X 45 , X 13 , X 23 , X 33 and X 43 are N and the others are CR. It may be in one aspect.
  • R in CR has the same meaning as R in the proviso of the compound represented by formula (1) described later.
  • the metal-organic structure As the metal-organic structure, the metal-organic structure of the present invention described in detail below is preferable.
  • the metal organic structure of the present invention contains at least one of group II to XIV elements as constituent elements and a compound represented by the following formula (1) as a ligand. Moreover, the metal organic structure may contain a halogen element as a constituent element. The constituent element here is not an element that constitutes a ligand.
  • the group II to XIV elements are preferably Zr, Cd, Ti, Cu, Zn, Fe, Cr, Ni, Co, Mo, Hf, Mg, Al and Si, more preferably Cu and Zn. , Cd.
  • Halogen elements include fluorine, chlorine, bromine and iodine.
  • composition formula of the metal-organic framework of the present invention is represented by, for example, Cu 4 I 4 L, where L is the ligand.
  • the ligand is coordinated to copper, for example, by one of the two nitrogen atoms of the ligand's pyrimidine ring.
  • Cu 4 I 4 is present, for example, in the Cuban form in the metal-organic framework of the invention.
  • a schematic diagram of the Cuban-type structure is shown in FIG.
  • Cuban-type structures are cubic, with Cu or I at each vertex, and the line segments between Cu and I constituting the edges.
  • Cu and Cu are not adjacent, and I and I are not adjacent.
  • Cu and Cu exist only on diagonal lines, and I and I also exist only on diagonal lines. Since Cu and I have different atomic sizes, the actual structure is not cubic but distorted.
  • ⁇ Cu-I-Cu is about 60° and ⁇ I-Cu-I is about 110°.
  • L in the figure represents a ligand.
  • Examples of the crystal system in the normal state of the metal-organic structure of the present invention include a tetragonal system.
  • Examples of the space group in the normal state of the metal-organic structure of the present invention include I4 1 /a.
  • FIG. 3 is a schematic diagram of the three-dimensional structure of an example of the metal-organic framework of the present invention (without carbon dioxide capture).
  • the first framework L1a represented by light gray spheres (atoms) and rods (bonds)
  • the second framework L1a represented by dark gray spheres (atoms) and rods (bonds) L2a interpenetrates to form an interpenetrating structure.
  • FIG. 4 is a schematic diagram of the three-dimensional structure of an example of the metal-organic framework of the present invention (with carbon dioxide capture).
  • the first framework L1a is represented by light gray spheres (atoms) and rods (bonds), and dark gray spheres (atoms) and rods (bonds) are represented.
  • the second framework L2a interpenetrate to form an interpenetrating structure.
  • carbon dioxide is also trapped in the isolated space formed by the two frameworks, represented by partially overlapping three spheres (corresponding to C and O, respectively).
  • X 11 and X 13 are N and X 12 , X 14 and X 15 are CR, or X 12 and X 14 are N and X 11 , X 13 and X 15 are CR; Or, X 11 and X 15 are N and X 12 , X 13 and X 14 are CR.
  • X 21 and X 23 are N and X 22 , X 24 and X 25 are CR, or X 22 and X 24 are N and X 21 , X 23 and X 25 are CR; Or, X 21 and X 25 are N and X 22 , X 23 and X 24 are CR.
  • X 31 and X 33 are N and X 32 , X 34 and X 35 are CR, or X 32 and X 34 are N and X 31 , X 33 and X 35 are CR; Or, X 31 and X 35 are N and X 32 , X 33 and X 34 are CR.
  • X 41 and X 43 are N and X 42 , X 44 and X 45 are CR, or X 42 and X 44 are N and X 41 , X 43 and X 45 are CR; Or, X 41 and X 45 are N and X 42 , X 43 and X 44 are CR.
  • Each R is independently a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl group is a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom).
  • R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl The group is optionally substituted with a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom.
  • the halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • the alkyl group and the alkyl group in the alkyloxy group may be linear, branched or cyclic.
  • the straight-chain and branched-chain alkyl groups preferably have 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
  • the number of carbon atoms in the cyclic alkyl group is preferably 3-30, more preferably 3-12, and particularly preferably 3-10.
  • R 1 to R 6 are an alkyl group or an alkyloxy group
  • the alkyl group in the alkyl group and the alkyloxy group is preferably linear in that it can impart an appropriate amount of steric hindrance to the benzene ring. .
  • alkyl groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and cyclohexyl group. , n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, 3,7-dimethyloctyl group, n-lauryl group and the like. Among these, methyl group, ethyl group, n-propyl group, iso-propyl group and n-butyl group are preferred.
  • the number of halogen atoms in the halogen-substituted alkyl group is not particularly limited.
  • alkyl groups substituted with halogen atoms include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.
  • alkyloxy groups include methyloxy, ethyloxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, tert-butyloxy, n-pentyloxy, n- hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, etc. mentioned.
  • a methyloxy group, an ethyloxy group, an n-propyloxy group, an iso-propyloxy group and an n-butyloxy group are preferred.
  • halogen atoms in the halogen-substituted alkyloxy group is not particularly limited.
  • alkyloxy groups substituted with halogen atoms include trifluoromethyloxy, pentafluoroethyloxy, perfluorobutyloxy, perfluorohexyloxy, perfluorooctyloxy, methyloxymethyloxy, 2- A methyloxyethyloxy group and the like can be mentioned.
  • the aryl groups of R and R 1 to R 6 may be unsubstituted.
  • Aryl groups may be substituted with halogen atoms.
  • the aryl group may be substituted with an alkyl group optionally substituted with a halogen atom.
  • the aryl group may be substituted with an alkyloxy group optionally substituted with a halogen atom.
  • the (unsubstituted) aryl group includes, for example, a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group and 9-anthracenyl group.
  • the aryl group substituted with a halogen atom includes, for example, a pentafluorophenyl group.
  • Examples of the aryl group substituted with an alkyl group optionally substituted with a halogen atom include, for example, a C1-C12 alkylphenyl group ("C1-C12" means having 1 to 12 carbon atoms. , is the same.) and the like.
  • the aryl group substituted with an alkyloxy group optionally substituted with a halogen atom includes, for example, a C1-C12 alkyloxyphenyl group.
  • An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon.
  • the aromatic hydrocarbons include those having condensed rings and those in which two or more selected from independent benzene rings and/or condensed rings are bonded directly or via a group such as vinylene.
  • R is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms optionally substituted by a halogen atom, an alkyloxy group having 1 to 3 carbon atoms optionally substituted by a halogen atom, and hydrogen Atoms are more preferred.
  • R 1 to R 6 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms optionally substituted by a halogen atom, and an alkyloxy group having 1 to 3 carbon atoms optionally substituted by a halogen atom. is preferred, and an optionally halogen-substituted alkyl group having 1 to 3 carbon atoms is more preferred.
  • Examples of X 11 to X 15 , X 21 to X 25 , X 31 to X 35 and X 41 to X 45 include the following combinations. (i): X 11 , X 13 , X 21 , X 23 , X 31 , X 33 , X 41 and X 43 are N and X 12 , X 14 , X 15 , X 22 , X 24 , X The combination wherein 25 , X32 , X34 , X35 , X42 , X44 , and X45 are CR.
  • Each R is independently a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl group is a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom).
  • R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkyloxy group optionally substituted with a halogen atom, or an aryl group (the aryl The group is optionally substituted with a halogen atom, an alkyl group optionally substituted with a halogen atom, or an alkyloxy group optionally substituted with a halogen atom. )
  • the method for producing the compound represented by formula (1) is not particularly limited.
  • a production method according to the synthesis reaction of the following scheme can be mentioned.
  • Y 1 to Y 4 are halogen atoms.
  • R 1 to R 6 have the same definitions as R 1 to R 6 in formula (1).
  • X 1 to X 5 have the same meanings as X 11 to X 15 , X 21 to X 25 , X 31 to X 35 and X 41 to X 45 in Formula (1). is. )
  • Palladium catalysts used in the reaction include, for example, [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (PdCl 2 (dppf)), tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ), bis(triphenylphosphine)dichloropalladium (Pd (PPh3)2Cl2), bis(benzylideneacetone)palladium (Pd(dba)2 ) , tris (benzylideneacetone)dipalladium ( Pd2 (dba) 3 ), bis(tri-tert-butylphosphine)palladium (Pd(Pt-Bu 3 ) 2 ), palladium acetate (Pd(OAc) 2 ), chloro[(tri-tert-butylphosphine]palladium(II) dichloride (PdCl 2 (d
  • the amount of the catalyst used may be a so-called catalytic amount, preferably 20 mol % or less, particularly preferably 10 mol % or less, relative to the compound represented by formula (1B).
  • the amount used may be a so-called catalytic amount, preferably 20 mol% or less, particularly preferably 10 mol% or less, relative to the compound represented by formula (1B). be.
  • a base is also used in the synthesis reaction, and examples of the base include hydroxides, alkoxides, fluoride salts, carbonates, phosphates, and fluoride salts.
  • hydroxides include sodium hydroxide, potassium hydroxide, cesium hydroxide and the like.
  • Alkoxides include, for example, tert-butoxysodium and tert-butoxypotassium.
  • fluoride salts include lithium fluoride, potassium fluoride, and cesium fluoride.
  • Carbonates include, for example, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate and the like.
  • Phosphates include, for example, potassium phosphate.
  • amines include trimethylamine, triethylamine, diisopropylamine, n-butylamine, diisopropylethylamine and the like.
  • the base is preferably carbonates or phosphates, more preferably potassium carbonate or cesium carbonate, from the viewpoint of efficiently obtaining the desired product.
  • the amount of the base used is preferably 1 to 20 mol, more preferably 2 to 10 mol, per 1 mol of formula (1B).
  • the solvent used in the synthesis reaction is not particularly limited as long as it does not adversely affect the reaction.
  • Specific examples thereof include aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic hydrocarbons, ethers, and amides. , lactams, lactones, alcohols, urea derivatives, sulfoxides, water and the like.
  • Examples of aliphatic hydrocarbons include pentane, n-hexane, n-octane, n-decane and decalin.
  • Halogenated aliphatic hydrocarbons include, for example, chloroform, dichloromethane, dichloroethane, carbon tetrachloride, and the like.
  • aromatic hydrocarbons examples include benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene and mesitylene.
  • Ethers include, for example, diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane and the like.
  • Amides include, for example, N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and the like.
  • Lactams include, for example, N-methylpyrrolidone.
  • Lactones include, for example, ⁇ -butyrolactone.
  • Alcohols include, for example, methanol, ethanol, propanol, and the like.
  • Urea derivatives include, for example, N,N-dimethylimidazolidinone and tetramethylurea.
  • Sulfoxides include, for example, dimethylsulfoxide, sulfolane, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the compound represented by formula (1A) and the compound represented by formula (1B) to be charged is 1 mol of the compound represented by formula (1A) per 1 mol of the compound represented by formula
  • the compound represented by (1B) is preferably 4 to 10 mol, more preferably 4.2 to 10 mol.
  • the reaction temperature of the synthesis reaction is appropriately set within a range from the melting point to the boiling point of the solvent, taking into consideration the types and amounts of the raw material compounds and catalysts to be used. 100°C.
  • the reaction time for the synthesis reaction varies depending on the raw material compounds used, the reaction temperature, and the like, and cannot be defined unconditionally, but is usually about 1 to 72 hours.
  • the synthesis reaction is preferably carried out in a state in which nitrogen is circulated in the reaction vessel.
  • the method for producing the metal-organic structure is not particularly limited, and a method known as a method for producing an MOF can be employed. , ionothermal method, high-throughput method, etc.), stepwise synthesis method (e.g., metal-organic nodular structure precursor complex method, complex ligand method, in-situ sequential synthesis method, post-synthesis modification method, etc.), sonochemical synthesis methods, mechanochemical synthesis methods, and the like.
  • the solvothermal method is preferred because a stable thermodynamic product can be obtained. Production of a metal organic framework using a solvothermal method can be performed, for example, with reference to literature (Shi-Bin Ren, et al. CrystEngComm, 2009, 11, 1834-1836).
  • a method for producing a metal organic framework containing the compound represented by formula (1), copper, and iodine using a solvothermal method will be described below.
  • a mixture of a compound represented by formula (1), copper (I) iodide, potassium iodide, and a solvent is heated.
  • Potassium iodide is used to improve the solubility of CuI in the solvent. Therefore, potassium iodide may not be used depending on the type of solvent and the type of ligand.
  • the compounding ratio of the compound (L) represented by formula (1) and copper (I) iodide (CuI) when producing the metal organic structure is not particularly limited, but the molar ratio (L: CuI), preferably 1:4 to 1:10, more preferably 1:4 to 1:6.
  • the amount of potassium iodide used in producing the metal organic structure is not particularly limited, but is preferably 10 to 100 mol, more preferably 30 to 80 mol, per 1 mol of copper (I) iodide.
  • a modulator may be used to promote crystallization, if desired, during the production of the metal-organic framework.
  • Modulators include, for example, triphenylphosphine, pyridinium hydrochloride, isoquinoline, and the like.
  • the amount of the modulator used in producing the metal organic structure is not particularly limited, but is preferably 0.5 to 10 equivalents, more preferably 1 to 5 equivalents, relative to the compound represented by formula (1). .
  • the solvent examples include N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), acetonitrile, formic acid, acetic acid, methanol, ethanol, water and mixed solvents of two or more thereof. but not limited to these. Among these, a mixed solvent of acetonitrile, ethanol, and water is preferred.
  • the amount of the solvent used when manufacturing the metal organic structure is not particularly limited.
  • the raw material solution may be placed in any sealed container, or the raw material solution may be heated while refluxing.
  • the heating temperature is not particularly limited, and may be, for example, 100° C. or higher or 120° C. or higher from the viewpoint of enhancing reactivity, or 150° C. or lower from the viewpoint of preventing steam leakage during the reaction. good.
  • the heating time is not particularly limited, and can be appropriately adjusted according to the heating temperature. From the viewpoint of completely completing the reaction, the heating time is, for example, 6 hours or longer, 10 hours or longer, 12 hours or longer, 18 hours or longer, 24 hours or longer, 30 hours or longer, 36 hours or longer, 42 hours or longer, and 48 hours. 54 hours or more, or 60 hours or more, and 96 hours or less, 84 hours or less, 72 hours or less, 60 hours or less, 48 hours or less, 24 hours or less, 12 hours or less, or 10 hours or less. you can
  • the obtained product may be appropriately post-treated.
  • the obtained product may be filtered.
  • a poor solvent or the like may be added to the filter cake obtained by filtration, and the mixture may be dispersed by heating at room temperature or as appropriate, and then filtered again.
  • the poor solvent may be a solvent in which the target metal-organic structure is difficult to dissolve, such as water, acetonitrile, hexane, ethanol, dimethylformamide, or the like.
  • the temperature for heating may be, for example, 40° C. or higher, 50° C. or higher, 60° C. or higher, 70° C. or higher, or 80° C. or higher, and 100° C. or lower, 90° C. or lower, or 80° C. or lower. It's okay.
  • the heating time for heating may be, for example, 1 hour or longer, 2 hours or longer, 6 hours or longer, 10 hours or longer, or 12 hours or longer, and may be 24 hours or shorter, or 16 hours or shorter.
  • the target metal organic structure can be obtained by appropriately drying the filter cake obtained by filtration or re-filtration.
  • the drying may be carried out under normal pressure or under reduced pressure, but from the viewpoint of improving efficiency, it is preferably carried out under reduced pressure.
  • the temperature for drying may be, for example, 20°C or higher, 25°C or higher, 40°C or higher, 50°C or higher, or 60°C or higher, and 100°C or lower, 90°C or lower, 80°C or lower, or 60°C or higher. °C or lower.
  • the drying time for drying may be, for example, 1 hour or longer, 2 hours or longer, 6 hours or longer, 10 hours or longer, or 12 hours or longer, and may be 24 hours or shorter, or 16 hours or shorter.
  • the use of the metal organic structure is not particularly limited, but a carbon dioxide scavenger is preferable because of its excellent carbon dioxide scavenger.
  • the carbon dioxide scavenger can be suitably used in a carbon dioxide storage system capable of storing carbon dioxide.
  • ⁇ NMR measurement conditions 1 H-NMR spectrum (400 MHz) and 13 C-NMR spectrum (400 MHz) were measured by JEOL JNM-ECA400II. A measurement sample was dissolved in heavy chloroform (CDCl 3 ) to which tetramethylsilane (TMS) was added. Chemical shifts were derived relative to TMS ( ⁇ 0.0 ppm).
  • the measured diffraction data were analyzed by Rigaku's software CrysAlisPro. (i) a crystal of the metal-organic framework [Cu 4 I 4 Lp] from which the solvent in the pores has been removed, and (ii) a single crystal of the crystal of the metal-organic framework [Cu 4 I 4 Lp] with CO 2 trapped.
  • X-ray diffraction data were measured at BL-5A at the Institute of Materials Structure Science (IMSS), High Energy Accelerator Research Organization (KEK), Synchrotron Radiation Facility (PF).
  • the measured diffraction data were integrated by the software XDS.
  • the crystals that captured CO 2 were immersed in oil and measured immediately after being taken out from the CO 2 atmosphere into the air.
  • Microtrac Bell's fully automatic gas adsorption measurement device BELSORP MAX was used to measure adsorption and desorption isotherms related to capture and desorption of nitrogen (77 K and 298 K) and carbon dioxide (273 K and 298 K) gases, respectively.
  • the sample was ground in a mortar, and about 60 mg was placed in a glass measurement container and attached to the measurement device.
  • the inside of the container was evacuated by a rotary pump and a turbomolecular pump, and the solvent in the pores was removed by heating at 473 K for 12 hours at 1 kPa or less.
  • the amount of adsorption was measured by the constant volume type gas adsorption method.
  • a fixed volume of gas is introduced into a measurement container, and the amount of adsorption (capture amount of gas) is calculated by detecting changes in the pressure of the gas.
  • An adsorption isotherm was created by increasing the amount of gas stepwise, and a desorption isotherm was obtained by reducing the pressure by vacuuming.
  • the measurement container was removed from the apparatus, and the mass of the sample (adsorbate) after solvent removal was determined by weighing using a precision balance.
  • the Dewar bottle was filled with liquid nitrogen, and at 273K or 298K, the antifreeze liquid filled in the water tank was circulated through an open cooling circulator to maintain the measured temperature.
  • the analysis program BEL MASTER TM was used to analyze the experimental results.
  • PXRD Powder X-ray diffraction
  • Example 1 A pyrimidine ligand (Lp) was synthesized based on the following synthetic scheme.
  • the resulting mixture was poured into water and the solid precipitate was removed by suction filtration and washed with water.
  • the pink solid was dissolved in chloroform (100 mL), the solution was washed with a saturated aqueous sodium thiosulfate solution, and iodine was removed by liquid separation.
  • the organic layer was dried with magnesium sulfate and dried under reduced pressure to obtain an orange solid.
  • the solid was washed with ethyl acetate and subjected to suction filtration to obtain the desired product as a white powder. Yield was 71%.
  • FIG. 5A is the unit cell
  • FIG. 5B is the structure of one molecule. It was confirmed from the single crystal structure that the desired compound was obtained. Also, the measured dihedral angle of the two central aromatic rings is 92.15°, which is almost perpendicular. It was found that this gave a similar ligand with d symmetry.
  • Example 2 ⁇ Synthesis of metal organic framework [Cu 4 I 4 Lp]> pyrimidine ligand (Lp) (11 mg, 0.020 mmol), copper (I) iodide (19 mg, 0.10 mmol), potassium iodide (0.83 g, 5.0 mmol), and triphenylphosphine (5.2 mg , 0.020 mmol), acetonitrile (5.4 mL), distilled water (3.6 mL), and ethanol (1 mL) were added in order, and heated in an oven at 140 ° C. for 64 hours. . After heating, the temperature was slowly lowered in the oven, and after half a day or more, it was taken out of the oven.
  • Acetonitrile is present in the pores of the metal organic framework [Cu 4 I 4 Lp] immediately after synthesis. In this state, FT-IR measurement, single crystal X-ray structure analysis, PXRD measurement, and adsorption isotherm measurement were performed.
  • FIGS. 7A to 7B The single crystal X-ray structure analysis results of the obtained metal organic framework [Cu 4 I 4 Lp] are shown in FIGS. 7A to 7B, FIGS. 8A to 8C, and FIGS. 9A to 9B.
  • the metal-organic framework [Cu 4 I 4 Lp] had a Cuban type as the metal connector.
  • the Cuban-type connector had a tetra-coordinated diamond structure like the ligand, and the structure as a whole formed a three-dimensional diamond structure.
  • Disordered acetonitrile was present as a solvent in the pores.
  • the packing structure is shown in FIGS. 8A-8C, but the solvent is not shown, indicating that there are pores where the solvent is.
  • this structure has an interpenetrating structure in which two frameworks interpenetrate.
  • the pore size was calculated by CCDC's Mercury and the pore size was 5.4 ⁇ 4.9 ⁇ 4.9 ⁇ in space with a porosity of 12%.
  • the passage between that space and other spaces was of a size that a sphere having a diameter corresponding to the Kinetic Diameter of gaseous helium (2.57 ⁇ ) could not pass through. Therefore, in the obtained metal organic framework [Cu 4 I 4 Lp], there are no passages through which substances can pass between the pores and other pores or between the pores and the outside. seen in That is, the pores of the obtained metal organic framework [Cu 4 I 4 Lp] were isolated spaces. This is believed to be due to the bulky structure of the ligand and the interpenetrating structure of the two frameworks.
  • Adsorption isotherms for gas trapping of the metal-organic framework [Cu 4 I 4 Lp] were determined. Results are shown in FIG. This result was obtained after removing the solvent (acetonitrile) from the crystals. The solvent is removed by the operation for gas adsorption measurement (the operation of evacuating the container with a rotary pump and a turbomolecular pump and heating at 473 K for 12 hours at 1 kPa or less). According to adsorption isotherms, the metal-organic framework [Cu 4 I 4 Lp] did not trap nitrogen gas, but specific trapping was observed in CO 2 . Also, hysteresis is observed in CO 2 capture/desorption.
  • a pore is an isolated space that is connected to the outside only through a passage through which a sphere with a diameter corresponding to the Kinetic Diameter of gaseous helium (2.57 ⁇ ) cannot pass, so nitrogen molecules with a Kinetic Diameter greater than that. is generally understood not to capture .
  • CO2 was captured and desorbed, suggesting that CO2 caused a conformational change in the metal-organic framework [ Cu4I4Lp ], creating channels through which CO2 could pass. .
  • FIG. 12 shows the result of crystallographic X-ray structure analysis of the metal organic framework [Cu 4 I 4 Lp] in the absence of acetonitrile.
  • Single crystal X-ray structure analysis confirmed that the single crystal after vacuum heating hardly retained the solvent. In addition, even after removing the solvent, the point group of the crystal structure did not change, and the size of the lattice did not change, so it was found that the structure was maintained.
  • BELSORP MAX was used for CO2 capture. Two spatulas of single crystals, solvent removed by vacuum heating, were added to the BELSORP measurement vessel. It was heated at 200° C. for 12 hours at 1 kPa or less by the same operation as the adsorption isotherm measurement. After heating, the vessel was evacuated and purged of CO2 . The vessel was left to stand for 1 day while being filled with CO 2 . A single crystal was removed from the container and transferred to a vial (5 mL). The crystals were stored under high CO2 concentration by blowing CO2 into the vial using a commercially available CO2 spray and immediately closing the lid.
  • FIG. 13 shows the results of single crystal X-ray structure analysis. A linear electron density distribution, which was not observed after solvent removal, was observed in the portion corresponding to the pores. It can be fitted as CO2 , suggesting that CO2 is trapped in the pores. Since this measurement was performed in air, it is believed that this structure captures CO2 even though it is not in a CO2 atmosphere.

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