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Guest-compound-enveloping polymer-metal-complex crystal, method for producing same, method for preparing crystal structure analysis sample, and method for determining molecular structure of organic compound NEW

外国特許コード F190009872
整理番号 AF11-08US2
掲載日 2019年7月29日
出願国 アメリカ合衆国
出願番号 201816217086
公報番号 20190137367
出願日 平成30年12月12日(2018.12.12)
公報発行日 令和元年5月9日(2019.5.9)
優先権データ
  • 特願2012-197911 (2012.9.7) JP
  • 特願2012-270199 (2012.12.11) JP
  • 2013JP56370 (2013.3.7) WO
  • 201514426809 (2015.3.9) US
発明の名称 (英語) Guest-compound-enveloping polymer-metal-complex crystal, method for producing same, method for preparing crystal structure analysis sample, and method for determining molecular structure of organic compound NEW
発明の概要(英語) The present invention is a method for preparing a crystal structure analysis sample in which a molecule of an organic compound for which a molecular structure is to be determined, is arranged in pores and voids of a polymer-metal complex crystal in an ordered manner. The method includes immersing a polymer-metal complex crystal including a guest compound in a solvent solution that includes the organic compound, the polymer-metal complex crystal including a guest compound being the polymer-metal complex crystal comprising a polymer-metal complex that comprises a ligand having two or more coordinating moieties. A ratio of an amount of the guest compound (A) present in the pores and the voids to a total amount of the guest compound included in the pores and the voids being 60 mol % or more.
従来技術、競合技術の概要(英語) BACKGROUND ART
In recent years, a physiologically active substance that is derived from a marine organism or the like and found in a trace amount has been expected to be a resource for agricultural chemicals, medicines, and the like (Patent Documents 1 and 2). Therefore, it has become very important to accurately and efficiently determine the molecular structure of such a trace amount of organic compound in order to develop a novel agricultural chemical or medicine, for example.
When producing an agricultural chemical or a medicine, it is necessary to accurately identify a trace amount of impurities included in the agricultural chemical, medicine, or raw material in order to improve safety.
It has also been desired to identify a trace amount of impurities included in a raw material used to produce electronic parts, and reduce the amount of impurities along with a recent improvement in performance of electronic parts.
Specifically, it has been desired to accurately and efficiently determine the molecular structure of a trace amount of organic compound in various fields.
X-ray single crystal structure analysis has been known as a method for determining the molecular structure of an organic compound. The molecular structure of an organic compound can be accurately determined using X-ray single crystal structure analysis when it is possible to prepare a high-quality single crystal.
However, when the amount of organic compound is very small, and it is impossible to obtain a sufficient amount of single crystal, it is difficult to employ X-ray single crystal structure analysis for determining the molecular structure of the organic compound. It is difficult to prepare a single crystal when the organic compound for which the molecular structure is to be determined is liquid at about room temperature (i.e., when the melting point of the organic compound is equal to or lower than room temperature).
RELATED-ART DOCUMENT
Patent Document
- Patent Document 1: JP-A-2006-232738
- Patent Document 2: JP-A-2010-090141
特許請求の範囲(英語) [claim1]
1. A method for preparing a crystal structure analysis sample in which a molecule of an organic compound for which a molecular structure is to be determined, is arranged in pores and voids of a polymer-metal complex crystal in an ordered manner, the method comprising:
immersing a polymer-metal complex crystal including a guest compound in a solvent solution that includes the organic compound,
the polymer-metal complex crystal including a guest compound being the polymer-metal complex crystal comprising a polymer-metal complex that comprises a ligand having two or more coordinating moieties, and a metal ion that serves as a center metal, the polymer-metal complex having a three-dimensional network structure that is formed by the metal ion and the ligand that is coordinated to the metal ion, and having pores and voids that are three-dimensionally arranged in the three-dimensional network structure in an ordered manner, at least one compound selected from a group consisting of an aliphatic hydrocarbon, an alicyclic hydrocarbon, an ether, an ester, an aromatic hydrocarbon, a halogenated hydrocarbon, and a nitrile being included in the pores and the voids as a guest compound (A), and
a ratio of an amount of the guest compound (A) present in the pores and the voids to a total amount of the guest compound included in the pores and the voids being 60 mol % or more.

[claim2]
2. The method for preparing a crystal structure analysis sample according to claim 1, the method comprising immersing the polymer-metal complex crystal including the guest compound (A) in the solvent solution that includes the organic compound in an amount of 100 μg or less so that a value A calculated by an expression (2) is 0.1 to 30,
A=ba(2)
where, b is an amount of the organic compound included in the solvent solution, and a is an amount of a substance having a specific gravity of 1 that is required to fill all of the pores and the voids of the polymer-metal complex crystal with the substance having a specific gravity of 1.

[claim3]
3. The method for preparing a crystal structure analysis sample according to claim 1, wherein a concentration of the organic compound in the solvent solution is 0.001 to 50 μg/μL.

[claim4]
4. The method for preparing a crystal structure analysis sample according to claim 1, wherein the organic compound is impurities included in a compound derived from a natural product, or a synthetic compound.

[claim5]
5. The method for preparing a crystal structure analysis sample according to claim 1, the method comprising volatilizing the solvent after immersing the polymer-metal complex crystal including a guest compound in the solvent solution that includes the organic compound to concentrate the solvent solution.

[claim6]
6. The method for preparing a crystal structure analysis sample according to claim 5, wherein a volatilization rate of the solvent is 0.1 to 1000 μL/24 hours.

[claim7]
7. The method for preparing a crystal structure analysis sample according to claim 5, wherein the solvent is volatilized at 0 to 180° C.

[claim8]
8. The method for preparing a crystal structure analysis sample according to claim 1, wherein the immersing of the polymer-metal complex crystal including a guest compound in the solvent solution that includes the organic compound includes immersing one piece of the polymer-metal complex crystal including a guest compound in the solvent solution that includes the organic compound.

[claim9]
9. The method for preparing a crystal structure analysis sample according to claim 1, the method comprising:
a step (I) that separates a mixture that includes an organic compound for which a molecular structure is to be determined, by liquid chromatography to obtain a solvent solution of the organic compound for which the molecular structure is to be determined; and
a step (II) that immerses the polymer-metal complex crystal including a guest compound in the solvent solution of the organic compound for which the molecular structure is to be determined, that has been obtained in the step (I), and volatilizes the solvent under moderate conditions to concentrate the solvent solution.

[claim10]
10. The method for preparing a crystal structure analysis sample according to claim 1, wherein a molecular structure of the resulting crystal structure analysis sample can be determined with a resolution of at least 1.5 Å by applying MoKα radiation (wavelength: 0.71 Å) generated at a tube voltage of 24 kV and a tube current of 50 mA to the crystal structure analysis sample, and detecting diffracted X-rays using a CCD detector.

[claim11]
11. The method for preparing a crystal structure analysis sample according to claim 1, wherein the guest compound (A) is an alicyclic hydrocarbon having 3 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 10 carbon atoms.

[claim12]
12. The method for preparing a crystal structure analysis sample according to claim 1, wherein the guest compound (A) is a saturated alicyclic hydrocarbon having 3 to 20 carbon atoms.

[claim13]
13. The method for preparing a crystal structure analysis sample according to claim 1, wherein a total occupancy ratio of the guest compound included in the pores and the voids of the polymer-metal complex is 10% or more.

[claim14]
14. The method for preparing a crystal structure analysis sample according to claim 1, wherein the ligand having two or more coordinating moieties is an organic ligand having three or more coordinating moieties, and the metal ion that serves as the center metal is a cobalt ion or a zinc ion.

[claim15]
15. The method for preparing a crystal structure analysis sample according to claim 1, wherein the polymer-metal complex is a compound represented by [[M(X)2]3(L)2]n (wherein M is a metal ion, X is a monovalent anion, L is a tridentate ligand represented by a formula (1),
wherein Ar is a substituted or unsubstituted trivalent aromatic group, X1 to X3 are independently a divalent organic group, or a single bond that directly bonds Ar and Y1, Y2, or Y3, and Y1 to Y3 are independently a monovalent organic group having a coordinating moiety, and n is an arbitrary natural number).

[claim16]
16. The method for preparing a crystal structure analysis sample according to claim 1, wherein the metal ion is an ion of a metal among the metals that belong to Groups 8 to 12 in the periodic table.

[claim17]
17. The method for preparing a crystal structure analysis sample according to claim 1, wherein the metal ion is a zinc(II) ion or a cobalt(II) ion.

[claim18]
18. The method for preparing a crystal structure analysis sample according to claim 1, wherein the polymer-metal complex crystal has a cubic or cuboidal shape with a side length of 10 to 1000 μm.

[claim19]
19. The method for preparing a crystal structure analysis sample according to claim 1, the method comprising immersing a polymer-metal complex crystal including a crystallization solvent in the guest compound (A) in a liquid state, or an inert solvent solution that includes the guest compound (A), the polymer-metal complex crystal including a crystallization solvent comprising a polymer-metal complex that comprises a ligand having two or more coordinating moieties, and a metal ion that serves as a center metal, the polymer-metal complex having a three-dimensional network structure that is formed by the metal ion and the ligand that is coordinated to the metal ion, and having pores and voids that are three-dimensionally arranged in the three-dimensional network structure in an ordered manner, a crystallization solvent (excluding the guest compound (A)) being included in the pores and the voids.

[claim20]
20. A method for determining a molecular structure of an organic compound comprising analyzing a crystal structure of a crystal structure analysis sample obtained using the method for preparing a crystal structure analysis sample according to claim 1 to determine a molecular structure of an organic compound included in the pores and the voids of the crystal structure analysis sample.
  • 発明者/出願人(英語)
  • Fujita Makoto
  • Inokuma Yasuhide
  • Yoshioka Shota
  • Ariyoshi Junko
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
国際特許分類(IPC)
参考情報 (研究プロジェクト等) CREST Development of the Foundation for Nano-Interface Technology AREA
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