Updated on 2024/05/23

写真b

 
SUGAMATA Koh
 
*Items subject to periodic update by Rikkyo University (The rest are reprinted from information registered on researchmap.)
Affiliation*
Graduate School of Science Master's Program in Chemistry
Graduate School of Science Doctoral Program in Chemistry
Title*
Specially Appointed Associate Professor
Degree
Doctor of Science ( 3 2012   Kyoto University )
Research Theme*
  • 有機無機材料化学・有機元素化学。環境調和型分子の開発を通じ、カーボンニュートラルな社会構築に貢献することを目標としている。非常に小さい細孔であるマイクロ孔を有する多孔性材料を活用した高効率なガス貯蔵分子の合成およびその応用を検討している。また、分子骨格への元素導入により特異な性質を有する新規有機分子の合成及びそれらの物性解析に関する研究にも取り組んでいる。

  • Campus Career*
    • 4 2022 - Present 
      Graduate School of Science   Master's Program in Chemistry   Specially Appointed Associate Professor
    • 4 2022 - Present 
      Graduate School of Science   Doctoral Program in Chemistry   Specially Appointed Associate Professor
    • 10 2017 - 3 2022 
      College of Science   Assistant Professor
     

    Research Areas

    • Nanotechnology/Materials / Organic functional materials

    Research History

    • 4 2022 - Present 
      Rikkyo University   College of Science Department of Chemistry   Project Associate Professor

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      Country:Japan

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    • 9 2023 - 10 2023 
      University of Tsukuba

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    • 10 2017 - 3 2022 
      RIKKYO UNIVERSITY   College of Science   Assistant Professor

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    • 4 2014 - 9 2017 
      Toyo University

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    • 4 2008 - 3 2009 
      多摩化学工業株式会社   研究開発部

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    Education

    • 4 2009 - 3 2012 
      Kyoto University   Graduate School of Sc   Department of Chemistry

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      Country: Japan

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    • 4 2006 - 3 2008 
      Kitasato University   Graduate School of Science

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    • 4 2002 - 3 2006 
      Kitasato University   School of Science

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    Papers

    • Reactivity of a Linear 2-Germapropadiene with Acids, Ketones, and Amines. Invited Peer-reviewed International journal

      Koh Sugamata, Teppei Asakawa, Mao Minoura

      Chemistry, an Asian journal   e202400262   22 4 2024

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      Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)  

      The reactivity of an isolable 2-germapropadiene with acids, ketones, and amines was investigated. The reactions of 2-germapropagiene 1 with hydrogen chloride and acetic acid afforded the corresponding dichlorogermane (2) and diacetoxygermane (3), respectively, indicating that the central germanium atom of 1 is electrophilic. The reaction of 1 with benzaldehyde proceeds via a formal [2+2] cycloaddition to afford the corresponding spiro compound (4). Moreover, 1 reacts smoothly with acetone to furnish germane 5, which contains a six-membered ring involving two acetone molecules. Furthermore, 1 undergoes N-H bond insertion with methylamine or aniline to afford diamino germanes 7 and 8, respectively. The reaction of 1 with urea selectively afforded the corresponding N-H-insertion product (8).

      DOI: 10.1002/asia.202400262

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    • Phosphoramide-Based Metal-Organic Frameworks for Effective Gas Adsorption. Peer-reviewed International journal

      Koh Sugamata, Sho Kobayashi, Natsuki Amanokura, Akihiro Shirai, Mao Minoura

      Chemistry A European Journal (Weinheim an der Bergstrasse, Germany)   e202400962   27 3 2024

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      Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)  

      Cost-effective and facile synthetic routes to organic ligands, along with porous materials that exhibit exceptional gas-storage properties, promise significant industrial applications. Here, a two-step synthesis of novel organophosphorus ligands without metal catalysts is reported. These ligands serve as versatile linkers for the construction of metal-organic frameworks (MOFs) incorporating various metal ions, including zinc and copper. One of the zinc-based MOFs demonstrates remarkable gas-storage properties, with a hydrogen (H2) capacity exceeding 2.5 wt% at 77 K and 100 kPa as well as a carbon dioxide (CO2) capacity exceeding 20 wt% at 298 K and 100 kPa. Furthermore, this zinc-based MOF can be synthesized through a solvothermal process on the gram scale that yields high-quality single crystals.

      DOI: 10.1002/chem.202400962

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    • [1]Ferrocenophane Bridged by a 9-Silafluorenylidene Moiety Peer-reviewed

      Shinnosuke Usuba, Koh Sugamata, Shogo Morisako, Takahiro Sasamori

      Inorganics12 ( 3 ) 66 - 66   22 2 2024

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      Publishing type:Research paper (scientific journal)   Publisher:MDPI AG  

      Sila[1]ferrocenophane bearing a 9-silafluorenylidene moiety (1) as a bridging unit was synthesized and isolated as a stable crystalline compound. Sila[1]ferrocenophane 1, which was newly obtained in this study, was characterized by spectroscopic analyses, a single-crystal X-ray diffraction (SC-XRD) analysis, and electrochemical measurements. Due to the characteristic 9-silafluorenyl moiety, 1 exhibited large electron affinity and a slightly higher oxidation potential relative to that of ferrocene. In addition, 1 was found to undergo ring-opening polymerization (ROP) triggered by thermolysis at a lower temperature relative to that of Ph2Sifc (1′, fc = 1,1′-ferrocenylidene). It also underwent ROP through reduction by KC8 to give the corresponding polymeric compound. The DFT calculations suggested that one-electron reduction of 1 would promote ring-opening polymerization, as shown in the experimental results.

      DOI: 10.3390/inorganics12030066

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    • Synthesis, structural analysis, and gas-adsorption properties of a dibenzothiophene-based hydroxamate/zinc metal-organic framework Peer-reviewed

      Koh Sugamata, Sho Kobayashi, Akihiro Shirai, Natsuki Amanokura, Mao Minoura

      Bulletin of the Chemical Society of Japan97 ( 3 )   14 2 2024

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      Authorship:Lead author, Corresponding author   Publishing type:Research paper (scientific journal)   Publisher:Oxford University Press (OUP)  

      Abstract

      We report the mixed-ligand synthesis of a novel hydroxamate/zinc metal-organic framework (MOF) with a dibenzothiophene scaffold. The reaction of dibenzothiophene-3,7-dicarbohydroxamic acid, isonicotinic acid, and zinc nitrate under solvothermal conditions afforded a porous hydroxamate/zinc MOF. The structure and gas-adsorption properties toward N2, H2, CO2, and CH4 of the hydroxamate/zinc MOF were investigated.

      DOI: 10.1093/bulcsj/uoae017

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      Other Link: https://academic.oup.com/bcsj/article-pdf/97/3/uoae017/56848919/uoae017.pdf

    • Alkoxy-Functionalized Hydroxamate/Zinc Metal-Organic Frameworks and the Effects of Substituents and Acid Addition on Their Structures. Peer-reviewed International journal

      Koh Sugamata, Yanhua Zhang, Natsuki Amanokura, Akihiro Shirai, Mao Minoura

      Inorganic chemistry63 ( 5 ) 2454 - 2459   5 2 2024

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      Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)  

      Single crystals of alkoxy-functionalized hydroxamate/zinc metal-organic frameworks (MOFs) were obtained by fixating the hydroxamate moiety via intramolecular hydrogen bonding. The resulting MOF structures depend on the steric demand of the alkoxy groups, whereby the incorporation of bulky isopropyl groups affords porous hydroxamate/zinc MOFs. The topological structures of the isopropyl-substituted MOFs could be controlled by adding acid.

      DOI: 10.1021/acs.inorgchem.3c03438

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    • A zirconium-based metal–organic framework with dibenzothiophene linkers: synthesis, structural analysis, and gas-adsorption properties Peer-reviewed

      Koh Sugamata, Sho Kobayashi, Natsuki Amanokura, Akihiro Shirai, Mao Minoura

      Journal of Coordination Chemistry76 ( 16-24 ) 1817 - 1824   5 12 2023

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      Authorship:Lead author, Corresponding author   Publishing type:Research paper (scientific journal)   Publisher:Informa UK Limited  

      DOI: 10.1080/00958972.2023.2287970

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    • Zn-Based Metal-Organic Frameworks Using Triptycene Hexacarboxylate Ligands: Synthesis, Structure, and Gas-Sorption Properties. Peer-reviewed International journal

      Koh Sugamata, Shoko Yamada, Daichi Yanagisawa, Natsuki Amanokura, Akihiro Shirai, Mao Minoura

      Chemistry (Weinheim an der Bergstrasse, Germany)29 ( 64 ) e202303417   16 11 2023

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      Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)  

      Invited for the cover of this issue is the group of Koh Sugamata, Mao Minoura, and co-workers at Rikkyo University. The image depicts triptycene-based metal-organic frameworks with honeycomb structures that collect carbon dioxide and hydrogen, in an analogy to bees collecting honey in their honeycombs. Read the full text of the article at 10.1002/chem.202302080.

      DOI: 10.1002/chem.202303417

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    • A Tin Analogue of Propadiene with Cumulated C=Sn Double Bonds

      Koh Sugamata, Teppei Asakawa, Mao Minoura

          24 8 2023

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      Authorship:Lead author, Corresponding author   Publisher:American Chemical Society (ACS)  

      The synthesis, structure, and properties of a stable, linear 2-stannapropadiene are reported. The identical C=Sn bonds in this 2-stannapropadiene are the shortest hitherto reported C–Sn bonds. This 2-stannapropadiene features a 119Sn NMR signal at 507 ppm for the central tin atom, indicative of an unsaturated SnIV oxidation state. Treatment of this 2-stannapropadiene with SnCl2·dioxane resulted in the formation of a novel four-membered cyclic 1,1-dichloro-1,3-distannetane.

      DOI: 10.26434/chemrxiv-2023-2d7rc

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    • Zn-Based Metal-Organic Frameworks Using Triptycene Hexacarboxylate Ligands: Synthesis, Structure, and Gas-Sorption Properties. Peer-reviewed International journal

      Koh Sugamata, Shoko Yamada, Daichi Yanagisawa, Natsuki Amanokura, Akihiro Shirai, Mao Minoura

      Chemistry A European Journal (Weinheim an der Bergstrasse, Germany)29 ( 64 ) e202302080   17 8 2023

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      A series of metal-organic frameworks (MOFs) based on zinc ions and two triptycene ligands of different size have been synthesized under solvothermal conditions. Structural analyses revealed that they are isostructural 3D-network MOFs. The high porosity and thermal stability of these MOFs can be attributed to the highly rigid triptycene-based ligands. Their BET specific surface areas depend on the size of the triptycene ligands. In contrast to these surface-area data, the H2 and CO2 adsorption of these MOFs is larger for MOFs with small pores. Consequently, we introduced functional groups to the bridge-head position of the triptycene ligands and investigated their effect on the gas-sorption properties. The results unveiled the role of the functional groups in the specific CO2 binding via an induced interaction between adsorbates and the functional groups. Excellent H2 and CO2 properties in these MOFs were achieved in the absence of open metal sites.

      DOI: 10.1002/chem.202302080

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    • 2-Heteraallenes. Peer-reviewed International journal

      Koh Sugamata, Takahiro Sasamori

      Dalton transactions (Cambridge, England : 2003)52 ( 29 ) 9882 - 9892   25 7 2023

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      While analogues of allenes with heavier main-group elements (group 14-16) have been extensively studied, 2-heteraallenes are rare chemical species whose properties are mostly unknown. It is also notable that the synthesis and isolation of allene-type molecules are not widespread, despite the extensive study of two-coordinated low-valent chemical species.

      DOI: 10.1039/d3dt01559a

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    • A Linear C=Ge=C Heteroallene with a Di-coordinated Germanium Atom. Peer-reviewed International journal

      Koh Sugamata, Teppei Asakawa, Daisuke Hashizume, Mao Minoura

      Angewandte Chemie (International ed. in English)62 ( 24 ) e202302836   12 6 2023

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      Allenes (>C=C=C<) are classified as cumulated dienes with a linear structure and an sp-hybridized central carbon atom. We have synthesized and isolated a stable 2-germapropadiene with bulky silyl substituents. The 2-germapropadiene allene moiety adopts a linear structure both in the solid state and in solution. An X-ray diffraction electron-density-distribution (EDD) analysis of this 2-germapropadiene confirmed the linear C=Ge=C geometry with a formally sp-hybridized germanium atom that bears two orthogonal C=Ge π-bonds. Based on detailed structural and computational studies, we concluded that the linear geometry of the isolated 2-germapropadiene most likely arises from the negative hyperconjugation of the silyl substituents at the terminal carbon atoms. The 2-germapropadiene reacts rapidly with nucleophiles, indicating that the linearly oriented germanium atom is highly electrophilic.

      DOI: 10.1002/anie.202302836

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    • Controlling the Flexibility of Carbazole-Based Metal-Organic Frameworks by Substituent Effects. Peer-reviewed International journal

      Koh Sugamata, Akihiro Shirai, Mao Minoura

      Chemistry A European Journal (Weinheim an der Bergstrasse, Germany)29 ( 25 ) e202203442   2 5 2023

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      We have developed highly porous Cu-based metal-organic frameworks (MOFs) using carbazole-type linkers. The novel topological structure of these MOFs was revealed by single-crystal X-ray diffraction analysis. Molecular adsorption/desorption experiments indicated that these MOFs are flexible and change their structure upon adsorption/desorption of organic solvents and gas molecules. These MOFs exhibit unprecedented properties that allow controlling their flexibility by adding a functional group onto the central benzene ring of the organic ligand. For example, the introduction of electron-donating substituents increases the robustness of the resulting MOFs. These MOFs also exhibit flexibility-dependent differences in gas-adsorption and -separation performance. Thus, this study represents the first example of controlling the flexibility of MOFs with the same topological structure via the substituent effect of functional groups introduced into the organic ligand.

      DOI: 10.1002/chem.202203442

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    • Synthesis and Structural Analysis of Organic Cyclic Polyselenides Obtained from the Reaction of a Bissilylcarbenoid with Selenium Peer-reviewed

      Koh Sugamata, Teppei Asakawa, Mao Minoura

      EUROPEAN JOURNAL OF INORGANIC CHEMISTRY26 ( 11 )   4 2023

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      Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-V C H VERLAG GMBH  

      The synthesis and isolation of the first examples of a tetraselenolane and a hexaselenepane, obtained from the reaction of a bissilylcarbenoid ((R2CBrLi)-C-Si; R-Si=SiMePh2) with elemental selenium, is reported. The molecular structures of these cyclic polyselenides were determined using single-crystal X-ray diffraction analysis. The selective synthesis of these polyselenides was achieved by controlling the reaction temperature. Stoichiometric deselenation of the hexaselenepane with triphenylphosphine afforded the corresponding tetraselenolane in quantitative yield. Further deselenation of the tetraselenolane with excess triphenylphosphine did not furnish the expected selenoketone but the diselenirane, as confirmed by spectroscopic analysis.

      DOI: 10.1002/ejic.202200780

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    • Synthesis of a Dibenzo-1,6,2,5-dioxadisilocine and Its Unexpected Reductive Coupling with Phenanthrene# Peer-reviewed

      Narumi Itoh, Koh Sugamata, Shogo Morisako, Shinobu Aoyagi, Hideki Yorimitstu, Takahiro Sasamori

      CHEMISTRY LETTERS52 ( 3 ) 177 - 180   3 2023

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

      A stable dibenzo-1,6,2,5-dioxadisilocine was synthesized as a difunctional electrophile for double-silylation reactions. Its molecular structure was fully characterized by spectroscopic means and single-crystal X-ray diffraction analysis. The reductive coupling with phenanthrene using a dispersion of sodium afforded an unexpected silylated polycyclic compound via a formal [3+3] dimerization of phenanthrene skeletons.

      DOI: 10.1246/cl.220478

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    • Development of Porous Coordination Polymers for Gas Storage and Separation Materials Invited Peer-reviewed

      Sugamata Koh, Shirai Akihiro, Minoura Mao

      Journal of Synthetic Organic Chemistry, Japan81 ( 1 ) 46 - 52   1 1 2023

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      Authorship:Lead author, Corresponding author   Language:Japanese   Publisher:The Society of Synthetic Organic Chemistry, Japan  

      Gas storage and separation are closely related to various aspects of human society, such as the alleviation of greenhouse effect, promoting clean energy, and controlling harmful gases. In particular, hydrogen has been enthusiastically researched as a clean energy source that emits no greenhouse gases. Therefore, there are requirements for safe methods to manufacture, store, and transport hydrogen. Conventionally, hydrogen storage materials are metal hydrides and metal amides that react violently with moisture, and their usage environments are limited by the extreme conditions required for hydrogen gas generation. Metal-organic frameworks (PCP/MOFs) are porous coordination materials that are composed of organic ligands and metal ions. Because of their ability to efficiently adsorb small molecules, PCP/MOFs have potential applications in e.g., gas adsorption, catalysis, as well as energy storage and conversion. Functionalization and modification of the organic ligands to construct new MOFs are fascinating and significant areas in crystal engineering owing to the potential applications of the resulting materials. We describe the synthesis and gas-adsorption properties of novel MOFs using the functionalized organic ligands.

      DOI: 10.5059/yukigoseikyokaishi.81.46

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    • Tellurium-Centered Bent Allenes: Synthesis, Characterization, and Reactivity. Peer-reviewed International journal

      Koh Sugamata, Teppei Asakawa, Yukiko Urao, Mao Minoura

      Inorganic chemistry61 ( 44 ) 17641 - 17645   7 11 2022

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      Compounds with multiple bonds between elements of the second and fifth periods are extremely unstable, and systematic investigations into their properties remain elusive. Herein, we report a tellurium-centered heteroallene that contains multiple bonds between carbon and tellurium. This compound is the first example of bis(methylene)-λ4-tellane, which was synthesized and fully characterized using multinuclear NMR spectroscopy and X-ray crystallography. In the solid state, this λ4-tellane exhibits a bent allene structure for the C═Te═C moiety and unsaturated Te-C bonds. Interestingly, the allene-type structure is retained in the solution, which is reflected in an absorption band due to the π-π* transition at 610 nm. This λ4-tellane also exhibits unique reactivity toward dihalogermylenes, which yielded rare cyclic telluragermetanes.

      DOI: 10.1021/acs.inorgchem.2c02697

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    • Three-Membered Rings With Two Heteroatoms Including Selenium or Tellurium; Three-Membered Rings With Three Heteroatoms Peer-reviewed

      Koh Sugamata, Shogo Morisako, Takahiro Sasamori

      Comprehensive Heterocyclic Chemistry IV   647 - 659   2022

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      Authorship:Lead author   Publishing type:Part of collection (book)   Publisher:Elsevier  

      DOI: 10.1016/b978-0-12-818655-8.00033-0

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    • Gas Adsorption in R<sub>2</sub>-MOF-5 Difunctionalized with Alkyl Groups Peer-reviewed

      Koh Sugamata, Sho Kobayashi, Teruyuki Iihama, Mao Minoura

      EUROPEAN JOURNAL OF INORGANIC CHEMISTRY2021 ( 31 ) 3185 - 3190   8 2021

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      Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-V C H VERLAG GMBH  

      Zinc terephthalate metal-organic framework (MOF) MOF-5 and some of its dialkylated derivatives (R-2-MOF-5; R=Me, Et, Pr, Bu) were obtained from a solvothermal synthesis using 2,5-dialkyl-1,4-benzenedicarboxylic acids with zinc nitrite. The effect of the solvent on the solvothermal synthesis of R-2-MOF-5 was investigated. For R=H and Me, interpenetrating or non-interpenetrating MOFs obtained depending on the choice of reaction solvent, while for R=Et, Pr, and Bu, no such solvent effect was observed, and only jungle-gym-type MOFs were generated. All compounds were fully characterized using powder X-ray diffraction analysis (PXRD), Fourier-transform infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA). After activation, all these compounds exhibit significant porosity, as confirmed by N-2-, H-2-, and CO2-sorption experiments. The N-2-adsorption capacity of these compounds depends on the size of the attached alkyl groups, while the H-2-uptake values tend to increase for the alkyl-functionalized MOFs relative to the unfunctionalized parent MOFs and exhibit a maximum value for Pr-2-MOF-5.

      DOI: 10.1002/ejic.202100466

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    • PCP/MOFの水素貯蔵量向上のための有機合成的アプローチ—Approach toward Improving Hydrogen Storage of PCP/MOF Using Synthetic Organic Chemistry—特集 社会実装のステージを迎えた水素貯蔵技術

      菅又 功, 白井 昭宏, 箕浦 真生

      水素エネルギーシステム = Journal of the Hydrogen Energy Systems Society of Japan / 水素エネルギー協会 編46 ( 4 ) 263 - 268   2021

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      Authorship:Lead author, Corresponding author   Language:Japanese   Publisher:水素エネルギー協会  

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    • Structural analysis of interpenetrated methyl-modified MOF-5 and its gas-adsorption properties. Peer-reviewed International journal

      Koh Sugamata, Daichi Yanagisawa, Keiko Awano, Teruyuki Iihama, Mao Minoura

      Acta crystallographica. Section C, Structural chemistry76 ( Pt 9 ) 845 - 849   1 9 2020

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      The first example of an interpenetrated methyl-modified MOF-5 with the formula Zn4O(DMBDC)3(DMF)2, where DMBDC2- is 2,5-dimethylbenzene-1,4-dicarboxylate and DMF is N,N-dimethylformamide (henceforth denoted as Me2MOF-5-int), namely, poly[tris(μ4-2,5-dimethylbenzene-1,4-dicarboxylato)bis(N,N-dimethylformamide)-μ4-oxido-tetrazinc(II)], [Zn4(C10H8O4)3O(C3H7NO)2]n, has been obtained from a solvothermal synthesis of 2,5-dimethylbenzene-1,4-dicarboxylic acid and Zn(NO3)2·6H2O in DMF. A systematic study revealed that the choice of solvent is of critical importance for the synthesis of phase-pure Me2MOF-5-int, which was thoroughly characterized by single-crystal and powder X-ray diffraction (PXRD), as well as by gas-adsorption analyses. The Brunauer-Emmett-Teller surface area of Me2MOF-5-int (660 m2 g-1), determined by N2 adsorption, is much lower than that of nonpenetrated Me2MOF-5 (2420 m2 g-1). However, Me2MOF-5-int displays an H2 uptake capacity of 1.26 wt% at 77 K and 1.0 bar, which is comparable to that of non-interpenetrated Me2MOF-5 (1.51 wt%).

      DOI: 10.1107/S2053229620010177

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    • Structural analysis of and selective CO2 adsorption in mixed-ligand hydroxamate-based metal-organic frameworks. Peer-reviewed International journal

      Koh Sugamata, Chikaze Takagi, Keiko Awano, Teruyuki Iihama, Mao Minoura

      Dalton transactions (Cambridge, England : 2003)49 ( 29 ) 9948 - 9952   7 8 2020

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      Two mixed-ligand metal-organic frameworks, [Zn2(BDHA)0.5(INA)3] (MOF-1: H2BDHA = benzene-1,4-dihydroxamic acid; HINA = isonicotinic acid) and [Co2(BDHA)0.5(INA)3(DMF)] (MOF-2), were solvothermally synthesized and fully characterized by single-crystal X-ray crystallography as well as N2, H2, and CO2 gas-sorption measurements. The results constitute the first detailed analysis of the bonding environment around the hydroxamates in such MOFs, which are simultaneously decorated with Lewis-basic sites from the hydroxamate moieties and metal sites predisposed for coordinative unsaturation. MOF-2 shows a desirably selective adsorption of CO2 relative to N2.

      DOI: 10.1039/d0dt01105c

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    • (Thio)(silyl)carbene and (seleno)(silyl)carbene gold(i) complexes from the reaction of bis(methylene)-λ<SUP>4</SUP>-sulfane and bis(methylene)-λ<SUP>4</SUP>-selane with chloro(dimethylsulfide)gold(i) Peer-reviewed International journal

      Koh Sugamata, Yukiko Urao, Mao Minoura

      DALTON TRANSACTIONS49 ( 23 ) 7688 - 7691   6 2020

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      Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

      The dinuclear (thio)(silyl)carbene and (seleno)(silyl)carbene gold(i) complexes1and2were obtained from the reaction of two equivalents of AuCl(SMe2) with the stable bis(methylene)-lambda(4)-chalcogenanes3and4, respectively. The reaction proceeds under elimination of the chlorosilane moiety of3and4. Complexes1and2were characterized by spectroscopic and X-ray diffraction (XRD) analyses. The(13)C NMR signals for the carbene centers of 1 (309 ppm) and 2 (345 ppm) are by more than 150 ppm downfield shifted relative to those for other known (NHC)AuCl complexes. These results indicate that (chalcogeno)(silyl)carbenes, like (amino)(silyl)carbenes, belong to the push-spectator family of carbenes.

      DOI: 10.1039/d0dt00967a

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    • Synthesis, Structure, and Reactivity of a Thermally Stable Dialkylgermylene Peer-reviewed

      Fumiaki Suzuki, Ryohei Nishino, Mariko Yukimoto, Koh Sugamata, Mao Minoura

      BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN93 ( 2 ) 249 - 251   2 2020

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

      The dialkylgermylene Trp*Ge-2: (Trp*: peripherally extended sterically demanding alkyl groups based on the triptycyl (Trp) framework), was obtained from the reaction of Trp*Li with GeCl2 center dot dioxane. The structure of Trp*Ge-2: was unequivocally determined by NMR and UV-vis spectroscopy, mass spectrometry, and a single-crystal X-ray diffraction analysis. Moreover, the reactivity of Trp*Ge-2: was examined.

      DOI: 10.1246/bcsj.20190338

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    • A stable bis(methylene)-λ<SUP>4</SUP>-selane with a >CSeC< bond containing Se(iv) Peer-reviewed

      K. Sugamata, Y. Urao, M. Minoura

      CHEMICAL COMMUNICATIONS55 ( 57 ) 8254 - 8257   7 2019

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      Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

      Bis(methylene)-lambda(4)-selane 1, which represents a new class of heteroallenes, was synthesized and isolated as a stable purple crystalline solid. X-ray crystallographic analysis revealed a bent allene-type structure with pseudo C-2v symmetry and a bent CSeC moiety that contains a 3-center-4-electron pi-bond. The NMR spectrum of 1 shows compelling evidence for a slow rotation of the SeC moieties at room temperature. The Se-77 NMR spectrum of 1 contains one signal in the region characteristic for Se(iv) compounds.

      DOI: 10.1039/c9cc04121d

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    • Systematic Synthesis and Crystal Structures of Tetraaryltellurium Compounds Ar<sub>4</sub>Te<SUP>IV</SUP> Peer-reviewed

      Sho Kobayashi, Koh Sugamata, Mao Minoura

      BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN92 ( 3 ) 661 - 663   3 2019

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

      Hypervalent tetraaryltellurium(IV) compounds of the type Ar4TeIV (1: Ar = C6H5; 2: Ar = p-H3CC6H4; 3: Ar = p-t-BuC6H4; 4: Ar = p-F3CC6H4) were prepared via a convenient one-pot reaction between the isolated corresponding ArLi reagent and TeCl4. X-ray crystallographic analyses of 1-4 revealed distortedpseudo-trigonal-bipyramidal (TBP) structures for Ar 4 Te and the TBP character was analyzed by the dihedral angle method.

      DOI: 10.1246/bcsj.20180380

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    • 30.3.7.11 Deprotection of S,S-Acetals (Update 2019) Peer-reviewed

      K. Sugamata, T. Sasamori

      Knowledge Updates 2019/2   2019

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      Authorship:Lead author   Publishing type:Part of collection (book)   Publisher:Georg Thieme Verlag  

      Abstract

      The use of S,S-acetals is increasingly popular as a strategy for the protection of carbonyl groups because, in comparison to the analogous acetals, they are chemically inert under many reaction conditions; this is due to the chemical softness of sulfur atoms. In this context, the deprotection of S,S-acetals to reveal the carbonyl group is of great importance. This update describes methods for the deprotection of S,S-acetals published between 2007 and 2017, and provides an update to Section 30.3.7.

      DOI: 10.1055/sos-sd-130-00297

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    • Synthesis of Ferrocenyl-Substituted Organochalcogenyldichlorogermanes Peer-reviewed

      Takahiro Sasamori, Yuko Suzuki, Koh Sugamata, Tomohiro Sugahara, Norihiro Tokitoh

      INORGANICS6 ( 3 )   9 2018

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:MDPI  

      Reaction of the isolable ferrocenyldichlorogermyl anion, Fc*GeCl2- (Fc* = 2,5-bis(3,5-di-t-butylphenyl)-1-ferrocenyl), with the isolable chalcogenenyl halides resulted in the formation of the corresponding organochalcogenyldichlorogermanes that were structurally characterized. Thus, it was demonstrated the use of sterically demanding ferrocenyl groups allowed isolating stable crystalline organochalcogenyldichlorogermanes.

      DOI: 10.3390/inorganics6030068

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    • Group 2 metal bis(arenecarbochalcogenoate)(crown ether) complexes: isolation and structural analysis. Peer-reviewed International journal

      Yoshiharu Tatematsu, Shinzi Kato, Norio Nakata, Masahiro Ebihara, Osamu Niyomura, Koh Sugamata, Mariko Yukimoto, Mao Minoura

      Dalton transactions (Cambridge, England : 2003)47 ( 29 ) 9787 - 9794   24 7 2018

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      Language:English   Publishing type:Research paper (scientific journal)  

      A series of Group 2 metal bis(arenecarbochalcogenoato)(crown ether) complexes M(EE'CAr)2(L)(L')x (M = Mg, Ca, Sr, Ba; Ar = aryl; E = S, Se; E' = O, S; L = H2O or THF; L' = 15-crown-5, 18-crown-6) were synthesized and their structures were revealed by X-ray analyses. The two carbothioato ligands in Mg, Ca and Sr 15-crown-5 complexes are located on the same side of the crown ether plane, while those in Mg, Ca, Sr, and Ba 18-crown-6 compounds are on both sides of the 18-crown-6 plane (trans relative to the plane). For the Ca 15-crown-5 complex, both carbothioato ligands are connected to the central Ca ion through an oxygen atom in a monodentate manner, and the two hydrogen atoms of the coordinated water molecule are intramolecularly hydrogen-bonded with thiocarbonyl sulfur atoms. One of the two carbothioate groups in the Ca 18-crown-6 complex is connected in a bidentate manner to the central metal, while the other is connected in a monodentate manner through an oxygen atom. The two thiocarboxylato ligands in the Sr 15-crown-5 congener are connected in a bidentate fashion to the same side of the crown ether plane. The Ca and Sr compounds are the first examples of alkali earth metal carbochalcogenoate complexes in which carbochalcogenolato ligands are connected in a monodentate manner through an oxygen atom. Both chalcogenoato ligands in Ba(SOCC6H4Me-4)2(18-crown-6) and Sr(SeOCC6H4Me-4)2(18-crown-6) are coordinated in a bidentate manner to the central metal ion.

      DOI: 10.1039/c8dt01959b

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    • Synthesis and Structure of a Stable Bis(methylene)-λ4 -sulfane. Peer-reviewed International journal

      Koh Sugamata, Daisuke Hashizume, Yuko Suzuki, Takahiro Sasamori, Shigeru Ishii

      Chemistry A European Journal (Weinheim an der Bergstrasse, Germany)24 ( 27 ) 6922 - 6926   11 5 2018

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      Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)  

      Bis(methylene)-λ4 -sulfane 1, a >C=S=C< heterocumulene, was obtained as a red crystalline solid from the reaction between elemental sulfur and a carbenoid that contains sterically demanding silylalkyl groups. Under atmospheric conditions, and even at elevated temperatures, 1 exhibits extraordinary stability. The molecular structure and electron-density distribution of 1 were analyzed by single-crystal X-ray diffraction analysis, which revealed a bent C=S=C geometry with C=S=C π-bonds. These results, combined with those of variable-temperature NMR measurements and theoretical calculations suggest a slow rotation of the S=C moieties in 1, the stability and structure of which were further examined by theoretical calculations.

      DOI: 10.1002/chem.201800828

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    • Synthesis of a Peripherally Extended Triptycyl Group as an Aliphatic Steric Protection Group and Its Application to the Kinetic Stabilization of an Aliphatic Sulfenic Acid Peer-reviewed

      Mariko Yukimoto, Ryohei Nishino, Fumiaki Suzuki, Michihiro Ishihara, Koh Sugamata, Mao Minoura

      CHEMISTRY LETTERS47 ( 4 ) 425 - 428   4 2018

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

      Trp*, a novel triptycene (Trp)-based aliphatic steric protection group was synthesized, and its potential to offer kinetic stabilization by steric protection was evaluated in the context of synthesizing a sulfenic acid (RSOH), i.e., a highly reactive sulfur-containing species. The isolated sulfenic acid Trp* SOH is thermally very stable, which clearly demonstrates the steric protection provided by Trp*.

      DOI: 10.1246/cl.171230

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    • Synthesis, Structure, and Thermolysis of Tris(dimethylphenylsilyl)methyl Sulfenyl Chloride Peer-reviewed

      Koh Sugamata, Shigeru Ishii

      CHEMISTRY LETTERS46 ( 6 ) 837 - 839   6 2017

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      Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

      Sulfenyl chlorides, i.e., di-coordinated sulfur(II) chlorides are useful precursors for a variety of organic sulfur compounds. Herein, the synthesis, structure, and reactivity of a sulfenyl chloride that bears a bulky tris(dimethylphenylsilyl) methyl group on the sulfur atom are reported. The thermolysis of this sulfenyl chloride resulted in the generation of the corresponding bissilylthioketone via the 1,2-elimination of chlorodimethyl-phenylsilane.

      DOI: 10.1246/cl.170188

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    • Selenium-Substituted Phosphaalkenes Obtained through 1,2-Elimination of Chlorosilanes from Selenenylchlorophosphines Peer-reviewed

      Takahiro Sasamori, Jose Manuel Villalba Franco, Jing-Dong Guo, Koh Sugamata, Shigeru Nagase, Rainer Streubel, Norihiro Tokitoh

      EUROPEAN JOURNAL OF INORGANIC CHEMISTRY ( 5 ) 678 - 684   2 2016

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-V C H VERLAG GMBH  

      Stable selenenyl-chlorophosphines, bearing a silylalkyl group, were synthesized. Subsequent treatment with Lewis acids such as AlCl3 afforded the corresponding phospha-alkenes. A reaction mechanism that proceeds through an intramolecular 1,2-elimination of chlorosilane was proposed.

      DOI: 10.1002/ejic.201500989

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    • Reaction of a diaryldigermyne with ethylene. Peer-reviewed International journal

      Takahiro Sasamori, Tomohiro Sugahara, Tomohiro Agou, Koh Sugamata, Jing-Dong Guo, Shigeru Nagase, Norihiro Tokitoh

      Chemical science6 ( 10 ) 5526 - 5530   1 10 2015

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      Language:English   Publishing type:Research paper (scientific journal)  

      Reaction of the stable digermyne BbtGe[triple bond, length as m-dash]GeBbt (Bbt = 2,6-[CH(SiMe3)2]2-4-[C(SiMe3)3]-C6H2) with ethylene initially afforded the corresponding 1,2-digermacyclobutene. Depending on the reaction conditions applied, further reaction of this 1,2-digermacyclobutene with ethylene furnished two different reaction products: a 1,4-digermabicyclo[2.2.0]hexane or a bis(germiranyl)ethane. Combined experimental and theoretical results suggested that the 1,4-digermabicyclo[2.2.0]hexane and the bis(germiranyl)ethane are the thermodynamic and kinetic reaction products, respectively. A reaction mechanism in agreement with these results was proposed.

      DOI: 10.1039/c5sc01266j

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    • Kinetically Stabilized Organophosphorus Radicals Peer-reviewed

      Sugamata Koh

      Journal of Synthetic Organic Chemistry, Japan73 ( 3 ) 276 - 277   2015

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      Authorship:Lead author, Corresponding author   Language:Japanese   Publisher:The Society of Synthetic Organic Chemistry, Japan  

      The organophosphorus radicals have drawn much attention in organic chemistry, biological processes, and functional materials due to their high reactivity. Although various species of organophosphorus radicals in solution have been observed by EPR spectroscopy, only a few examples have been isolated in the solid state. By using suitable bulky substituents, isolation of organophosphorus radicals such as dialkylphosphinyl radical, triarylphosphine radical cation, and tetraaryldiphosphine radical cation were achieved. The EPR spectra of those radicals showed the spin density of their radicals are mainly localized on phosphorus atom.

      DOI: 10.5059/yukigoseikyokaishi.73.276

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    • ChemInform Abstract: Unique Synthetic Approach Toward a Phosphaalkene: Synthesis of a Selenium-Substituted Phosphaalkene with Bulky Substituents. Peer-reviewed

      Koh Sugamata, Takahiro Sasamori, Norihiro Tokitoh

      ChemInform45 ( 32 ) no   7 2014

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      Publisher:Wiley  

      DOI: 10.1002/chin.201432205

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    • Unique Synthetic Approach toward a Phosphaalkene: Synthesis of a Selenium-substituted Phosphaalkene with Bulky Substituents Peer-reviewed

      Koh Sugamata, Takahiro Sasamori, Norihiro Tokitoh

      CHEMISTRY LETTERS43 ( 1 ) 95 - 96   1 2014

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      Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

      A selenium-substituted phosphaalkene, (Me3Si)(2)C=PSeTrp (1, Trp: 9-triptycyl), was synthesized by two methods, substitution reaction of (Me3Si)(2)C=PCl (3) with TrpSeLi, and treatment of TsiP(Cl)SeTrp (4, Tsi: C(SiMe3)(3)) with a catalytic amount of AlCl3. The newly, obtained phosphaalkene was characterized in detail.

      DOI: 10.1246/cl.130862

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    • Generation of an Organotellurium(II) Cation Peer-reviewed

      Koh Sugamata, Takahiro Sasamori, Norihiro Tokitoh

      EUROPEAN JOURNAL OF INORGANIC CHEMISTRY ( 5 ) 775 - 778   2 2012

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      Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-V C H VERLAG GMBH  

      We expected that the chemical trapping products of low-coordinated tellurenyl cation species can also be kinetically stabilized by the Tbt or Bbt group. Recently, we have reported the halogenation reactions of Bbt-substituted ditelluride, BbtTeTeBbt, leading to the formation of the Te-II-Te-IV mixed-valent tellurenyl fluoride, BbtTeTe(F)(2)Bbt, and tellurenyl halides, BbtTeX (X = Cl, Br, I). During the dehalogenation reactions of these tellurium halides, it is rational to postulate the formation of a tellurenyl cation species as an intermediate. In this paper, we report the successful trapping of tellurenyl cation species with butadienes or triphenylphosphane, and the regeneration of the tellurenyl cation species by thermal retro [1+4] cycloaddition of the diene adducts.

      DOI: 10.1002/ejic.201101313

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    • Fluorination reaction of a ditelluride bearing bulky aryl substituents: formation of mixed-valent Te(IV)-Te(II) ditelluride difluoride. Peer-reviewed International journal

      Koh Sugamata, Takahiro Sasamori, Norihiro Tokitoh

      Chemistry, an Asian journal6 ( 9 ) 2301 - 3   5 9 2011

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      Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)  

      DOI: 10.1002/asia.201100368

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    • Halogenation Reactions of a Ditelluride Having Bulky Aryl Groups Leading to the Formation of Organotellurium Halides Peer-reviewed

      Takahiro Sasamori, Koh Sugamata, Norihiro Tokitoh

      HETEROATOM CHEMISTRY22 ( 3-4 ) 405 - 411   2011

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-BLACKWELL  

      Halogenation reactions of BbtTe-TeBbt (Bbt; 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris (trimethylsilyl)methyl]phenyl) with SO2Cl2, Br-2, and I-2 were examined. When 1 equiv of the reagents were used, the corresponding tellurium monohalides were obtained as stable crystalline compounds. Although iodination reaction of BbtTe-TeBbt using 3 equiv of I-2 afforded BbtTeI, treatment of BbtTe-TeBbt with 3 equiv of SO2Cl2 and Br-2 gave the corresponding tellurium trthalides, BbtTeX(3)(X = Cl, Br), as stable crystalline compounds. Characterization of the obtained tellurium mono- and trihalides was achieved by the spectroscopic and crystallographic analyses, together with theoretical calculations. (C) 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:405-411, 2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20698

      DOI: 10.1002/hc.20698

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    Research Projects

    • 高周期典型元素を中心とする集積二重結合化合物の創製と未踏高反応性分子の開拓

      日本学術振興会  科学研究費助成事業 

      菅又 功

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      4 2024 - 3 2027

      Grant number:24K08388

      Grant amount:\4680000 ( Direct Cost: \3600000 、 Indirect Cost:\1080000 )

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    • Synthesis of heavier main-group element-centered heteroallene type molecules and their systematic property elucidation

      Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research 

      Sugamata Koh

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      4 2020 - 3 2023

      Grant number:20K05468

      Grant amount:\4290000 ( Direct Cost: \3300000 、 Indirect Cost:\990000 )

      Recently, we have successfully synthesized and isolated of the first sulfur-
      and selenium-centered allene-type bis(methylene)sulfane and bis(methylene)selane as stable compounds. In the present study, synthesis and properties of bis(methylene)tellane have been achieved by the reaction of bis(silyl)carbenoid with elemental tellurium.

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    • Development of novel heterocumulenes for the formations of multi-substituted heterocyclic compounds

      Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research 

      SUGAMATA Koh

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      4 2018 - 3 2020

      Grant number:18K14204

      Grant amount:\4160000 ( Direct Cost: \3200000 、 Indirect Cost:\960000 )

      Recently, we have successfully synthesized and isolated of the first sulfur- and selenium-centered allene-type bis(methylene)sulfane and bis(methylene)selane as stable compounds. In the present study, the reactions of these bis(methylene)chalcogenanes with HCl and halogenation reagents such as SO2Cl2 and Br2 afforded the corresponding 1,3-adducts quantitatively. Unexpectedly, the reactions of chalcogen-centered heteroallenes with AuCl(SMe2) gave the stable (thio) and (seleno)(silyl)carbene gold(I) complexes.

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    Industrial property rights

    • ジフェニルメタン骨格を有するカルボン酸イオンを配位子とする金属有機構造体

      箕浦 真生, 菅又 功, 小林 翔, 中江 智子, 松橋 泰典, 白井 昭宏

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      Applicant:学校法人立教学院

      Application no:特願2023-115329  Date applied:13 7 2023

      Announcement no:特開2024-012177  Date announced:25 1 2024

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    • カルバゾール骨格を有するカルボン酸イオンを配位子とする金属有機構造体

      箕浦 真生, 菅又 功

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      Applicant:学校法人立教学院

      Application no:特願2023-113443  Date applied:11 7 2023

      Announcement no:特開2024-012144  Date announced:25 1 2024

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    • ジベンゾチオフェン骨格を有するヒドロキサム酸イオンを有機配位子とする金属有機構造体

      箕浦 真生, 小林 翔, 菅又 功, 白井 昭宏

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      Applicant:学校法人立教学院

      Application no:特願2022-113004  Date applied:14 7 2022

      Announcement no:特開2024-011188  Date announced:25 1 2024

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