無機化学研究室 [ 半田 真 教授・池上崇久 准教授・片岡祐介 助教] 研 究 テ ー マ (発表論文(最近 5 年間)) 金 属 ― 金 属 結 合 を 含 む 二 核 錯 体 を 連 結 し た 新 規 機 能 性 高 分 子 錯 体 の 開 発 分子内に金属-金属結合を含むランタン型二核錯体は 頑丈で特異な電子状態を有している。この二核錯体を架 橋配位子で連結させた高分子錯体は、一般的な金属錯体 では見られない特異な磁性や電導性を示す事を確認して いる。また、それらの高分子錯体の集積によって形成さ れる微小な細孔は、オングストローム単位で微調整が可 能である為、分子サイズ選択性を備えたガス吸着挙動を 示す。 Synthesis, structures, and properties of lantern-type dinuclear ruthenium(II,III) complexes cis-[Ru2{3,5-(CF3)2-pf}2(O2CMe)2Cl] and [Ru2{3,5-(CF3)2-pf}3 (O2CMe)Cl], 3,5-(CF3)2-pf– = N,N’-bis[3,5-bis(trifluoromethyl)phenyl]formamidinate anion, Y. Harada, T. Ikeue, Y. Ide, Y. Kimura, I. Hiromitsu, D. Yoshioka, M. Mikuriya, Y. Kataoka, and M. Handa, Inorg. Chim. Acta, 2015, 424, 186-193. Synthesis and Crystal Structure of a Chain Complex of Molybdenum(II) Benzoate with 1,2-Bis(4-pyridyl)ethylene Having an N2-Adsorption Property, M. Mikuriya, N. Kaihara, T. Ono, Y. Tanaka, D. Yoshioka, H. Tanaka, and M. Handa, X-ray Struct. Anal. Online, 2014, 30, 41-42. Synthesis and Crystal Structure of a Chain Complex of Molybdenum(II) Benzoate and 1,2-Bis(4-pyridyl)ethane with an N2-Adsorption Property, M. Mikuriya, N. Kaihara, T. Ono, Y. Tanaka, D. Yoshioka, H. Tanaka, and M. Handa, X-ray Struct. Anal. Online, 2014, 30, 39-40. Molecule-Based Magnetic Compounds made up from Dinuclear Ruthenium(II,III) Carboxylate and Dicyanidoargentate(I), M. Mikuriya, Y. Tanaka, D. Yoshioka, and M. Handa, J Supercond. Nov. Magn, 2014, 27. Mixed-metal complexes of moxed-valent dinuclear ruthenium(II,III) carboxylate and tetracyanidonickelate(II), M. Mikuriya, Y. Tanaka, D. Yoshioka, and M. Handa, Chem. J. Mold. 2014, 9, 93-99. Crystal Structure and 1H NMR Spectral Property of a Lantern-Type Diruthenium(II,III) Complex with One Formamidinato and Three Acetato Bridges, M. Handa, T. Ikeue, M. Iida, D. Yoshioka, and M. Mikuriya, X-ray Struct. Anal. Online, 2014, 30, 31-32. Synthesis and Crystal Structure of a Chain Complex of Molybdenum(II) Benzoate and 4,4′-Bipyridyl in Relation to the N2-Adsorption Property,M. Mikuriya, N. Tsukimi, T. Ono, Y. Tanaka, D. Yoshioka, H. Tanaka, and M. Handa , X-ray Struct. Anal. Online, 2014, 30, 25-26. Synthesis and Crystal Structure of Aqua Adduct of Dinuclear Ruthenium(II,III) 3,4,5-Tri(ethoxy-d5)benzoate Tetrafluoroborate, H. Ishida, M. Handa, and M. Mikuriya, X-ray Struct. Anal. Online, 2014, 30, 9-10. Synthesis and Crystal Structure of a Chain Complex of Rhodium(II) Benzoate and 1,4-Diazabicyclo[2.2.2]octane having an N2-Adsorption Property, M. Mikuriya, J. Yamamoto, K. Ouchi, D. Yoshioka, H. Tanaka, and M. Handa, X-ray Struct. Anal. Online, 2013, 29, 45-46. Synthesis, Crystal Structure, and Nitorgen-Gas-Adsorption Property of Chain Complex of Dinuclear Rhodium(II) Benzoate and Ethylenediamine, M. Mikuriya, K. Ouchi, Y. Nakanishi, D. Yoshioka, H. Tanaka, and M. Handa, The Proceedings of the 1st International Porous and Powder Materials Symposium and Exhibition PPM 2013, ed. by Sevgi Kilic Ozdemir, Mehmet Polat, and Metin Tanoglu, Uc Adim printing House, Izmir, 2013, pp. 669-673. Synthesis and Crystal Structure of a Chain Complex of Molybdenum(II) Acetate and trans-1,2-Bis(4-pyridyl)ethylene in Relation to the N2-Adsorption Property, M. Mikuriya, S. Takada, D. Yoshioka, H. Tanaka, and M. Handa, X-ray Struct. Anal. Online, 2013, 29, 33-34. Synthesis and Crystal Structure of a Chain Complex of Molybdenum(II) Acetate and 1,2-Bis(4-pyridyl)ethane Aiming at N2-Adsorption Property, M. Mikuriya, N. Kaihara, J. Yamamoto, S. Takada, D. Yoshioka, H. Tanaka, and M. Handa, X-ray Struct. Anal. Online, 2013, 29, 31-32. Synthesis and Crystal Structure of a Chain Complex of Rhodium(II) Acetate and 1,2-Bis(4-pyridyl)ethane Having an N2-Adsorption Property, M. Mikuriya, J. Yamamoto, K. Ouchi, S. Takada, D. Yoshioka, H. Tanaka, and M. Handa, X-ray Struct. Anal. Online, 2013, 29, 29-30. Fastener effect on magnetic properties of chain compounds of dinuclear ruthenium carboxylates, H. Ishida, M. Handa, I. Hiromitsu, and M. Mikuriya, Chem. Papers, 2013, 67, 743-750. T. Ikeue, Y. Kimura, K. Karino, M. Iida, T. Yamaji, I. Hiromitsu, T. Sugimori, D. Yoshioka, M. Mikuriya, and M. Handa, Inorg. Chem. Commun., 2013, 33, 133-137. Structural, magnetic, and 1H NMR spectral study on lantern-type cis- and trans-diruthenium(II,III) complexes with two formamidinato and two acetato bridges, M. Handa, T. Ikeue, Y. Harada, Y. Kimura, T. Nishimura, D. Yoshioka, and M. Mikuriya, Crystal Structure of N,N’-Bis(3,5-dichlorophenyl)formamidine, X-ray Struct. Anal. Online, 2013, 29, 25-26. Synthesis, Crystal Structure, and N2-adsorption Property of a Chain Complex of Rhodium(II) Benzoate and Piperazine, M. Mikuriya, K. Ouchi, Y. Nakanishi, D. Yoshioka, H. Tanaka, and M. Handa, X-ray Struct. Anal. Online, 2013, 29, 21-22. Synthesis, Crystal Structure, and N2-adsorption Property of a Chain Complex of Rhodium(II) Acetate and 1,4-Diazabicyclo[2.2.2]octane, M. Mikuriya, J. Yamamoto, K. Ouchi, D. Yoshioka, H. Tanaka, and M. Handa, X-ray Struct. Anal. Online, 2013, 29, 7-8. Synthesis and Crystal Structure of a Rhodium(II) Formamidinate Dimer with Axial Water and Methanol Molecules, M. Handa, R. Inoue, A. Inoue, T. Nakai, T. Ikeue, D. Yoshioka, and M. Mikuriya, X-ray Struct. Anal. Online, 2012, 28, 53-54. Polymer Complex of Rhodium(II) Formamidinate Dimer Linked by 1,4-Diisocyanobenzene with Toluene as Crystal Solvent, M. Handa, A. Sanaka, Y. Sugikawa, T. Ikeue, H. Tanaka, D. Yoshioka, and M. Mikuriya, X-ray Struct. Anal. Online, 2011, 27, 73-74. Preparation and Crystal Structure of Chain Complex of Dinuclear Rhodium(II) Benzoate and Bipyrimidine with Diacetonitrile Adduct of Dinuclear Rhodium(II) Benzoate, M. Mikuriya, J. Yamamoto, K. Ouchi, D. Yoshioka, and M. Handa, X-ray Struct. Anal. Online, 2011, 27, 69-70. Synthesis and Crystal Structure of Rhodium(II) Pentafluorobenzoate Dimer with Axial Methanol Molecules, M. Handa, Y. Ishitobi, K. Moriyama, T. Ikeue, D. Yoshioka, and M. Mikuriya, X-ray Struct. Anal. Online, 2011, 27, 49-50. Synthesis and Crystal Structure of Chain Complex of Rhodium(II) Pivalate and trans-1,2-Bis(4-pyridyl)ethylene with an N2-Adsorption Property, M. Mikuriya, J. Yamamoto, D. Yoshioka, H. Tanaka, and M. Handa, X-ray Struct. Anal. Online, 2011, 27, 27-28. Synthesis, Crystal Structures, and Adsorption Properties of Chain Complexes of Rhodium(II) Pivalate with N,N’-bidentate ligands, M. Mikuriya, J. Yamamoto, D. Yoshioka, H. Tanaka, and M. Handa, in “New Trends in Coordination, Bioinorganic and Applied Inorganic Chemistry,” ed. by M. Melnik, P. Segla, and M. Tatarko, Slovak University of Technology Press, Bratislava, 2011, 311-319. Assembled Complexes of Lantern-type Rhodium(II) Dimers with Formamidinato Ligands, M. Handa, T. Ikeue, A. Sanaka, T. Nakai, H. Tanaka, D. Yoshioka, and M. Mikuriya, in “New Trends in Coordination, Bioinorganic and Applied Inorganic Chemistry,” ed. by M. Melnik, P. Segla, and M. Tatarko, Slovak University of Technology Press, Bratislava, 2011, 133-139. Molecule-based magnetic materials based on dinuclear ruthenium carboxylate and octacyanotungatate, M. Mikuriya, D. Yoshioka, A. Borta, D. Luneau, D. Matoga, J. Szklarzewicz, and M. Handa, New J. Chem., 2011, 35, 1226-1233. Crystal Structure of Rhodium(II) Formamidinate Dimer with an Axial Acetonitrile Molecule, M. Handa, M. Yasuda, D. Yoshioka, T. Ikeue, and M. Mikuriya, X-ray Structure Analysis Online, 2011, 27, 15-16. Preparation and crystal structure of tetrakis(m-pivalato-O,O’)bis[(pivalic acid-O)rhodium(II)], M. Mikuriya, J. Yamamoto, H. Ishida, D. Yoshioka, and M. Handa, X-ray Structure Analysis Online, 2011, 27, 7-8. Synthesis, crystal structure, and 1H NMR spectra of a chloride-bridged chain complex of dinuclear ruthenium(II,III) 3,4,5-tri(ethoxy-d5)benzoate, H. Ishida, M. Handa, T. Ikeue, J. Taguchi, and M. Mikuriya, Chem. Papers, 2010, 64, 767-775. フタロシアニンやポルフィリンを利用した太陽電池や光線力学治療の色素材料の合成 フタロシアニンやポルフィリンは、強い吸収帯を持って O いることから、色素材料として注目を集めている。これら の能力を利用して、色素増感太陽電池の色素材料の開発を 行っている。また、癌治療の一つである光線力学療法(PDT) などの色素材料の開発を目的としている。また、光触媒と して用いて活性酸素を発生させることで、環境汚染物質の O O N O O N N N M N N N O N O N O N N N M N N N O N O O O 分解などへの応用の検討をする。 A carboxylate Zn-phthalocyanine inhibits fibril formation of Alzheimer’s amyloid b peptide, S. Tabassum, A. M. Sheikn, S. Yano, T. Ikeue, M. Handa, and A Nagai, FFBS Journal, in press. Synthesis and magnetic properties of an annulated dinuclear copper(II) phthalocyanine peripherally having 2,6-dimethylphenoxy substituents, T. Ikeue, N. Sawada, N. Matsumoto, A. Miyazaki, T. Sugimori, M. Koikawa, I. Hiromitsu, K. Yoshino, M. Mikuriya, Y. Kataoka, and M. Handa, J. Porphyrins Phthalocyanines, 2014, 18, 708-714. Crystal Structure of the (2,3,12,13-Tetrabromo-5,10,15,20- tetraphenylporphyrinato)oxidovanadium(IV) Complex, T. Ikeue, N. Murai, Y. Hiraoka, T. Kubota, K. Omata, D. Yoshioka, M. Mikuriya, and M. Handa, X-ray Struct. Anal. Online, 2014, 30, 37-38. Homo- and Hetero-Dinuclear Nickel(II), Copper(II), and Oxidovanadium(IV) Complexes of a Schiff-Base-Fused Phthalocyanine with 2,6-Dimethylphenoxy and t-Butyl Groups, T. Ikeue, T. Fukahori, T. Mitsumune, K. Ueda, K. Fujii, S. Kurahashi, M. Koikawa, T. Sugimori, I. Hiromitsu, K. Yoshino, M. Mikuriya, and M. Handa, Inorg. Chim. Acta, 2014, 409, 433-440. Formation and characterization of five- and six-coordinate iron(III) corrolazine complexes, S. Kurahashi, T. Ikeue, T. Sugimori, M. Takahashi, M. Mikuriya, M. Handa, A. Ikezaki, and M. Nakamura, J. Porphyrins Phthalocyanines, 2012, 16, 518-529. Photo-catalytic Activity of Cationic Zinc(II) Complexes of Phthalocyanine and Porphyrazine Derivatives Loaded on the Surface of Silica Gel, K. Kasuga, H. Irie, H. Tanaka, T. Ikeue, T. Sugimori, and M. Handa, J. Phorphyrins Phthalocyanines, 2011, 15, 1078-1084. Benzoannelation Stabilizes the dxy1 State of Low-Spin Iron(III) Porphyrinates, T. Ikeue, M. Handa, A. Chambelin, A. Ghosh, O. Onayi, M. G. H. Vincente, A. Ikezaki, and M. Nakamura, Inorg. Chem., 2011, 50, 3567-3581. Mononuclear and Dinuclear Nickel(II) Complexes of an Octadentate Ligand Planarly Arranging Pc- and Salen-like Coordination Units with Bulky 2,6-Dimethylphenoxy and t-Butyl Groups, T. Ikeue, T. Fukahori, T. Sugimori, and M. Handa, in “New Trends in Coordination, Bioinorganic and Applied Inorganic Chemistry, “ed. by M. Melnik, P. Segla, and M. Tatarko, Slovak University of Technology Press, Bratislava, 2011, 183-189. Luminescence of tetraphenylporphyrin by an energy transfer from phtotexcited ZnO nanaparticle, I. Hiromitsu, A. Kawami, S. Tanaka, S. Morito, R. Sasai, T. Ikeue, Y. Fujita, and M. Handa, Chem. Phys. Lett., 2011, 501, 385-389. Annulated dinuclear palladium(II) phthalocyanine complex as an effective photo-oxidation catalyst for near-infrared region light, T. Ikeue, M. Sonoda, S. Kurahashi, H. Tachibana, D. Teraoka, T. Sugimori, K. Kasuga, and M. Handa, Inorg. Chem. Commun., 2010, 13, 1170-1172. 金属錯体を基盤とした人工光合成システムの開発と多角形金属錯体の機能 人工光合成システムによる水の光分解反応は、エネルギー として期待されている水素を得る為の理想的な手法である。 我々は、ロジウム二核錯体を基盤とした人工光合成システム が「世界最高クラスの水素発生効率」を示す事を明らかにし た。現在、更に優れた光触媒システムの開発に着手している。 また、ループ状、三角形、四角形及び球状の金属錯体を合成 し、触媒・分子篩・薬剤としての機能性を模索する。 Photo-Catalytic Activity of α-PbO2-type TiO2, H. Murata, Y. Kataoka, T. Kawamoto, I. Tanaka and T. Taniguchi, Phys. Status Solidi (RRL) – Rapid Rep. Lett., in press. Photochemical Production of Hydrogen from Water using Microporous Porphyrin Coordination Lattices, K. Sato, Y. Kataoka, W. Mori, Journal of Nanoscience and Nanotechology, 2012, 12, 585-590. Modification of MOF Catalysts by Manipulation of Counter-ions: Experimental and Theoretical Studies of Photochemical Hydrogen Production from Water over Microporous Diruthenium (II, III) Coordination Polymers, Y. Kataoka, Y. Miyazaki, K. Sato, T. Saito, Y. Nakanishi, Y. Kitagawa, T. Kawakami, M. Okumura, K. Yamaguchi, W. Mori, Supramolecular Chemistry 2011, 23, 287-296. Photocatalytic Hydrogen production from water using Heterogeneous Two-dimensional Rhodium Coordination Polymer [Rh2(p-BDC)2]n, Y. Kataoka, K. Sato, Y. Miyazaki, Y. Suzuki, H. Tanaka, Y. Kitagawa, T. Kawakami, M. Okumura, W. Mori, Chemistry Letters 2010, 39, 358-359. Photocatalytic hydrogen production from water using porous material [Ru2(p-BDC)2]n, Y. Kataoka, K. Sato, Y. Miyazaki, K. Masuda, H. Tanaka, S. Naito, W. Mori, Energy & Environmental Science 2009, 2, 397-400. その他 Efficient hydrolytic cleavage of plasmid DNA by chloro-cobalt(II) complexes based on sterically hindered pyridyl tripod tetraamine ligands: synthesis, crystal structure and DNA cleavage activity, S. S. Massoud, R. S. Perkins, F. R. Louka, W. Xu, A. L. Roux, Q. Dutercq, R. C. Fischer, F. A. Mautner, M. Handa, Y. Hiraoka, G. L. Kreft, T. Bortolotto and H. Terenzi, Dalton Trans., 2014, 43, 10086-10103. Synthesis, crystal structures, spectral, electrochemical and magnetic properties of di-µ-phenoxido-bridged dinuclear copper(II) complexes with N-salicylidene-2-hydroxybenzylamine derivatives: axial coordination effect of dimethyl sulphoxide molecule,Y. Kakuta, N. Masuda, M. Kurushima, T. Hashimoto, D. Yoshioka, H. Sakiyama, Y. Hiraoka, M. Handa, and M. Mikuriya, Chem. Papers, 2014, 68, 623-931. 主な共同研究者 御厨正博 先生(関西学院大学理工学部教授) 広光一郎 先生(島根大学大学院総合理工学研究科教授) 杉森 保 先生(富山大学大学院医薬准教授) 小俣 光司 先生(島根大学大学院総合理工学研究科教授) 田中秀和 先生(島根大学大学院総合理工学研究科教授) 小俣 光司 先生(島根大学大学院総合理工学研究科教授) 久保田 岳志 先生(島根大学大学院総合理工学研究科准教授) 長井 篤 先生(島根大学医学部教授) 中村幹夫 先生(東邦大学名誉教授) 川本達也(神奈川大学理学部教授) D. Luneau 先生(リヨン第1大学(フランス)教授) S. S. Massoud 先生(ルイジアナ大学ラファイエット校(アメリカ)教授) D. Matoga 先生(ヤゲロニアン大学(ポーランド)准教授) 研究室活動(2014 年) 錯体化学討論会で(中央大学(東京)、9/18-20) 日本化学会中国四国支部大会で(山口大学(山口)、11/8-9) 研究室対抗ソフトボール大会で(島根大学、11/24)
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