Updated on 2021/07/03

写真b

 
MATSUSHITA Nobuyuki
 
*Items subject to periodic update by Rikkyo University (The rest are reprinted from information registered on researchmap.)
Affiliation*
College of Science Department of Chemistry
Graduate School of Science Field of Study: Chemistry
Graduate School of Science Field of Study: Chemistry
Title*
Professor
Degree
理学博士 ( 1989   京都大学 ) / 理学修士 ( 1986   京都大学 )
Contact information
Mail Address
Research Theme*
  • 錯体化学・固体物性化学。色や光物性、その他固体物性が、光、温度、圧力、溶媒、ガス、pHなど外部刺激に応答して変化する遷移金属錯体(フォトクロミック金属錯体やベイポクロミック金属錯体など)に関して、金属錯体の合成から、構造解析、物性測定・解析、物性と構造の相関の考察、仕組みの解明まで一貫した研究を行っている。

  • Research Interests
  • 固体物性

  • 物性化学

  • 錯体化学

  • 結晶学

  • Chemistry

  • Campus Career*
    • 4 2009 - Present 
      College of Science   Department of Chemistry   Professor
    • 4 2009 - Present 
      Graduate School of Science   Field of Study: Chemistry   Professor
    • 4 2009 - Present 
      Graduate School of Science   Field of Study: Chemistry   Professor
     

    Research Areas

    • Nanotechnology/Materials / Functional solid state chemistry

    • Nanotechnology/Materials / Inorganic/coordination chemistry

    Research History

    • 4 2009 - Present 
      RIKKYO UNIVERSITY   College of Science Department of Chemistry   Professor

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    • 4 2007 - 3 2009 
      The University of Tokyo   Graduate School of Arts and Sciences

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    • 4 1997 - 3 2007 
      The University of Tokyo   Graduate School of Arts and Sciences

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    • 5 1996 - 3 1997 
      ドイツ・マールブルグ大学   文部省在外研究員

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    • 6 1989 - 3 1997 
      The University of Tokyo   College of Arts and Sciences

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    Education

    • - 3 1989 
      Kyoto University   Graduate School, Division of Natural Science

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      Country: Japan

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    • - 3 1986 
      Kyoto University   Graduate School, Division of Natural Science

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      Country: Japan

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    • - 3 1984 
      Kobe University   Faculty of Science   Department of Chemsitry

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      Country: Japan

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    Committee Memberships

    • 3 2010 - 3 2011 
      日本化学会   化学教育協議会 幹事会・役員会メンバー

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      Committee type:Academic society

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    • 3 2010 - 3 2011 
      日本化学会   化学教育協議会広報室長

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      Committee type:Academic society

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    • 3 2009 - 3 2011 
      日本化学会   化学教育協議会 「化学と教育」誌 投稿幹事会委員

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      Committee type:Academic society

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    • 3 2009 - 2 2010 
      日本化学会   化学教育協議会 「化学と教育」誌 編集委員会 レーダーWG 副主査

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      Committee type:Academic society

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    • 3 2007 - 2 2010 
      日本化学会   化学教育協議会 「化学と教育」誌 編集委員会委員

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      Committee type:Academic society

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    • 3 2008 - 2 2009 
      日本化学会   化学教育協議会 「化学と教育」誌 編集委員会 レーダーWG 主査

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      Committee type:Academic society

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    • 3 2006 - 2 2008 
      日本化学会   関東支部代議員

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      Committee type:Academic society

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    • 4 2000 - 3 2006 
      日本結晶学会   編集委員会委員

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      Committee type:Academic society

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    • 3 2001 - 2 2005 
      日本化学会   化学教育協議会 高校化学グランプリ・国際化学オリンピック委員会 委員

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      Committee type:Academic society

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    • 10 2001 - 11 2002 
      錯体化学会   第52回錯体化学討論会実行委員会 委員

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      Committee type:Academic society

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    Papers

    • Core–shell metal–macrocycle framework (MMF): spatially selective dye inclusion through core-to-shell anisotropic transport along crystalline 1D-channels connected by epitaxial growth Peer-reviewed

      Shohei Tashiro, Shinya Mitsui, David W. Burke, Ryou Kubota, Nobuyuki Matsushita, Mitsuhiko Shionoya

      CrystEngComm22 ( 8 ) 1306 - 1309   2020

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      Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry (RSC)  

      <p>Core–shell porous metal–macrocycle frameworks were fabricated <italic>via</italic> an epitaxial growth procedure to observe core-to-shell anisotropic transport of a dye.</p>

      DOI: 10.1039/d0ce00120a

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    • Unique Hydration/Dehydration-Induced Vapochromic Behavior of a Charge-Transfer Salt Comprising Viologen and Hexacyanidoferrate(II) Peer-reviewed

      Rikako Tanaka, Atsushi Okazawa, Hisashi Konaka, Akito Sasaki, Norimichi Kojima, Nobuyuki Matsushita

      Inorganic Chemistry57 ( 4 ) 2209 - 2217   19 2 2018

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      Authorship:Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society  

      We successfully prepared and crystallographically characterized the first intermolecular charge-transfer (CT)-based vapochromic compound, (EV)(H3O)2[Fe(CN)6] (1-Wet, EV2+: 1,1′-diethyl-4,4′-bipyridine-1,1′-diium), an ethyl viologen-containing CT salt. 1-Wet, which is purple in color, is transformed into a brown powder (1-Dry) upon exposure to methanol vapor, drying over silica gel, or heating
      1-Dry returns to 1-Wet upon exposure to water vapor. These color changes are induced by hydration and dehydration, and gravimetric analyses suggest that 1-Dry is the dehydrated form of 1-Wet, namely, (EV)(H)2[Fe(CN)6]. Interestingly, desorption of water molecules from the oxonium ions in 1-Wet produces isolated protons (H+) that remain in 1-Dry as counter cations. Powder X-ray crystal structure analysis of 1-Dry reveals the presence of very short contacts between the nitrogen atoms of adjacent [Fe(CN)6]4- anions in the crystal. The isolated protons are trapped between the nitrogen atoms of cyanido ligands to form very short N···H···N hydrogen bonds. A detailed comparison of the crystal structures of 1-Wet and 1-Dry reveals that hydration and dehydration induce changes in crystal packing and intermolecular CT interactions, resulting in reversible color changes.

      DOI: 10.1021/acs.inorgchem.7b03100

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    • A one-dimensional iodido-bridged Pt<sup>II</sup>/Pt<sup>IV</sup> mixed-valence complex cation with a hydrogen sulfate counter-anion Peer-reviewed

      Nobuyuki Matsushita

      Acta Crystallographica Section E: Crystallographic CommunicationsE74   1821 - 1825   2018

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

      DOI: 10.1107/S2056989018016158

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    • Ionic crystal containing protons (H+) As counter cations: Preparation and crystal structure of a salt of 4,4¤-bipiperidine-1,1¤-diium and hexacyanidoferrate(II) Peer-reviewed

      Rikako Tanaka, Atsushi Okazawa, Norimichi Kojima, Nobuyuki Matsushita

      Chemistry Letters47 ( 6 ) 697 - 699   2018

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      Authorship:Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Chemical Society of Japan  

      A molecular salt with a bulky cation and anion, (H2bipip)-(H)2[Fe(CN)6] (1) (H2bipip2+: 4,4¤-bipiperidine-1,1¤-diium), has been prepared. The salt comprises protons (H+) as counter cations. Single-crystal X-ray structure analysis revealed that the proton is trapped between two cyanido ligands of [Fe(CN)6]41 anions, forming a very short N£H+£N hydrogen bond.

      DOI: 10.1246/cl.180157

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    • Preparation and characterization of a μ-P<sub>2</sub>O<sub>7</sub>-μ-HPO<sub>4</sub> dinuclear Fe<sub>2</sub>(III, III) complex Peer-reviewed

      Yuji Miyazato, Kouta Imaizumi, Rikako Tanaka, Tohru Wada, Nobuyuki Matsushita

      Bulletin of the Chemical Society of Japan91 ( 5 ) 787 - 789   2018

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:Chemical Society of Japan  

      The [{Fe(Me3tacn)}2(-P2O7)(-HPO4)]12H2O dinuclear Fe2(III, III) complex was prepared. The HPO4 2 bridge in the complex arises from hydrolysis of the pyrophosphate bound to the Fe(III) centers in the trinuclear [{Fe(Me3tacn)}3- (P2O7)2]+ intermediate. Electrochemical reduction of this complex at pH &lt
      3.2 results in dissociation of the H2PO4 bridge.

      DOI: 10.1246/bcsj.20170427

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    • trans-Bis[2-(aminomethyl)pyridine-κ<sup>2</sup>N,N’]platinum(II) ] bis(hexafluoridophosphate) Peer-reviewed

      Hajime Nishimura, Nobuyuki Matsushita

      IUCrData3   x181236   2018

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

      DOI: 10.1107/S2414314618012361

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    • Unusual Ionic Bond and Solubility Mechanism of Na(n)PQQ (n=0-4) Crystals Peer-reviewed

      Kazuto Ikemoto, Yuki Sakamoto, Rikako Tanaka, Koji Ogata, Nobuyuki Matsushita, Shinichiro Nakamura

      CRYSTAL GROWTH & DESIGN17 ( 8 ) 4118 - 4123   8 2017

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

      A comparative study of van der Waals and ionic crystals can provide vital information for the medical and food industries. In this work, we investigated the coenzyme pyrroloquinoline quinone (PQQ), which contains three carboxyl groups coupled to imidazole, pyridine, and quinone. Whole-crystal analysis (crystal-ome) was attempted for Na(n)PQQ (n = 04) crystals. All deprotonation sites were found to be dependent on pK(a) except for the Na sites, which cannot be explained by pK(a). The Na(1)PQQ crystal exhibited an unusual ionic bond, forming COOH-Na+ at one of the carboxyl sites in the structure. The difference in the solubility of the van der Waals and ionic crystals was also investigated, with a focus on the dissolution processes of Na(0)PQQ and Na(2)PQQ, by combining molecular dynamics simulations with experiments that define the crystal surfaces. This study is the first step toward developing a general rule to link the different types of crystal structures with different dissolution mechanisms and rates.

      DOI: 10.1021/acs.cgd.7b00324

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    • A charge-transfer salt composed of methyl viologen and hexacyanidoferrate(II) Peer-reviewed

      Rikako Tanaka, Nobuyuki Matsushita

      ACTA CRYSTALLOGRAPHICA SECTION C-STRUCTURAL CHEMISTRY73   476 - 480   6 2017

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      Authorship:Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:INT UNION CRYSTALLOGRAPHY  

      The methyl viologen dication, used under the name Paraquat as an agricultural reagent, is a well-known electron-acceptor species that can participate in chargetransfer (CT) interactions. The determination of the crystal structure of this species is important for accessing the CT interaction and CT-based properties. The title hydrated salt, bis(1,1'-dimethyl-4,4'-bipyridine-1,1'-diium) hexacyanidoferrate(II) octahydrate, (C12H14N2)(2)[Fe(CN)(6)]center dot 8H(2)O or (MV)(2) [Fe(CN)(6)]center dot 8H(2)O [M (2+) is the 1,1'-dimethyl-4,4'-bipyridine-1,1'-diium (methyl viologen) dication], crystallizes in the space group P21/c with one MV2+ cation, half of an [Fe(CN)(6)](4-) anion and four water molecules in the asymmetric unit. The Fe II atom of the [Fe(CN)(6)](4-) anion lies on an inversion centre and has an octahedral coordination sphere defined by six cyanide ligands. The MV2+ cation is located on a general position and adopts a noncoplanar structure, with a dihedral angle of 40.32 (7)degrees between the planes of the pyridine rings. In the crystal, layers of electron-donor [Fe(CN)(6)](4-) anions and layers of electronacceptor MV2+ cations are formed and are stacked in an alternating manner parallel to the direction of the -2a + c axis, resulting in an alternate layered structure.

      DOI: 10.1107/S2053229617007616

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    • A one-dimensional bromide-bridged PtII/PtIV mixed-valence complex with a 2-bromoethanesulfonate counter-ion Peer-reviewed

      Nobuyuki Matsushita, Ayako Taira, Yoshiya Taoka

      Acta Crystallographica Section E: Crystallographic Communications73   1108 - 1112   2017

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:International Union of Crystallography  

      The title salt, catena-poly[[[bis(ethylenediamine)platinum(II)]-μ-bromido-[bis(ethylenediamine)platinum(IV)]-μ-bromido] tetrakis(2-bromoethanesulfonate) dihydrate], {[PtIIPtIV Br2(C2H8N2)4]C2H4BrSO3)4·2H2O}n, crystallizes in the space group P21212. It has a linear chain structure extending parallel to the c axis, composed of square-planar [Pt(en)2]2+ and elongated octahedral trans-[PtBr2(en)2]2+ cations (en is ethylenediamine) stacked alternately and bridged by the Br atoms. The Pt site of the [PtII/IV(en)2] unit is located on a general position. The Br site, which is also located on a general position, is equally disordered over two positions. The Pt and Br atoms form a slight zigzag ⋯Br - PtIV - Br⋯PtII⋯ chain, with PtIV - Br bond lengths of 2.453 (2) and 2.491 (3) Å, PtII⋯Br contacts of 3.069 (2) and 3.032 (3) Å, and PtIV- Br⋯PtIIangles of 178.06 (13) and 177.70 (13)°. The mixed-valence state of the Pt site is expressed by the parameter δ = (PtIV-Br)/(PtII⋯Br), with values of 0.799 and 0.822 for the two independent Br atoms. In the crystal, N - H⋯O and O - H⋯O hydrogen bonds between the amine groups of the Pt complex chains, the sulfonate groups and water molecules of crystallization, stabilize the cationic columnar structure.

      DOI: 10.1107/S2056989017009598

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    • Crystal structure of bis(1-ethylpyridinium) dioxonium hexacyanidoferrate(II) Peer-reviewed

      Rikako Tanaka, Nobuyuki Matsushita

      Acta Crystallographica Section E: Crystallographic Communications73   219 - 222   2017

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:International Union of Crystallography  

      The title compound, (C7H10N)2(H3O)2[Fe(CN)6] or (Etpy)2(H3O)2[Fe(CN)6] (Etpy+ is 1-ethylpyridinium), crystallizes in the space group Pnnm. The FeII atom of the [Fe(CN)6]4- anion lies on a site with site symmetry..2/m, and has an octahedral coordination sphere defined by six cyanido ligands. Both the Etpy+ and the oxonium cations are located on a mirror plane. In the crystal, electron-donor anions of [Fe(CN)6]4- and electron-acceptor cations of Etpy+ are each stacked parallel to the b axis, resulting in a columnar structure with segregated moieties. The crystal packing is stabilized by a three-dimensional O - H⋯N hydrogen-bonding network between the oxonium ions and the cyanide ligands of [Fe(CN)6]4-.

      DOI: 10.1107/S2056989017000810

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    • Crystal structure of dichlorido(1,2-phenylenediamine-κ2 N,N′)platinum(II) Konno Yosuke Peer-reviewed

      Yosuke Konno, Nobuyuki Matsushita

      Acta Crystallographica Section E: Crystallographic Communications73   1009 - 1012   2017

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      Authorship:Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:International Union of Crystallography  

      The PtII atom in the title compound, [PtCl2{(C6H4)(NH2)2}], lies on a twofold rotation axis and has a slightly distorted square-planar coordination environment defined by two N atoms of an 1,2-phenylenediamine ligand and two Cl- ions. In the crystal, the planar complex molecules are stacked parallel to the c axis, resulting in a columnar structure. In a column, an infinite almost straight Pt·Pt chain is formed, suggesting weak metal-metal interactions [Pt·Pt = 3.3475 (8) Å]. The crystal packing is stabilized by a three-dimensional N-H·Cl hydrogen-bonding network between the amino groups and the Cl ligands of adjacent molecules.

      DOI: 10.1107/S2056989017008477

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    • Dichlorido(o-phenylenediamine)palladium(II) Peer-reviewed

      Konno Y, Matsushita N

      IUCrData2   x170144   2017

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      DOI: 10.1107/S2414314617001444

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    • Potassium tetracyanidoaurate(III) monohydrate: a redetermination Peer-reviewed

      Matsushita N, Noguchi W, Tanaka R

      IUCrData2   x170382   2017

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      DOI: 10.1107/S2414314617003820

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    • Synthesis and Characterization of an Ru-2(III, IV) Complex Containing Pyrophosphate Bridge Peer-reviewed

      Yuji Miyazato, Tohru Wada, Masaaki Ohba, Nobuyuki Matsushita

      CHEMISTRY LETTERS45 ( 12 ) 1388 - 1390   12 2016

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      We prepared a new Ru-2(III, IV) complex containing a pyrophosphate as the dinucleating component, by the reaction between the mononuclear complex [Ru(Me(3)tacn)Cl-3] and Na4P2O7 center dot 10H(2)O in aqueous solution. Cyclic voltammetric measurement for the complex [{Ru(Me(3)tacn)}(2)(mu-O)(mu-P2O7)]PF6 (1) in aqueous solution revealed the formation of two species with higher oxidation states, such as [O=Ru(IV)Ru(IV)=O] and [O=Ru(IV)Ru(V)=O](+). Furthermore, this complex showed activity for water oxidation reaction with Ce(NH4)(2)(NO3)(6) as the chemical oxidant in acidic aqueous solution.

      DOI: 10.1246/cl.160721

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      Other Link: http://orcid.org/0000-0003-1022-430X

    • A one-dimensional chloride- bridged Pt-II/Pt-IV mixed-valence complex with a 4-[(4-hydroxyphenyl)diazenyl]benzenesulfonate counter-ion Peer-reviewed

      Nobuyuki Matsushita, Ayako Taira

      ACTA CRYSTALLOGRAPHICA SECTION C-STRUCTURAL CHEMISTRY71   1033 - +   12 2015

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:INT UNION CRYSTALLOGRAPHY  

      The title compound, catena-poly[[[bis(ethylenediamine-kappa N-2,N')platinum(II)]-mu-chlorido-[bis(ethylenediamine)platinum(IV)]-mu-chlorido] tetrakis{4-[(4-hydroxyphenyl)diazenyl]benzenesulfonate} dihydrate], {[(PtPtCl2)-Pt-II-Cl-IV(C2H8N2)(4)](HOC6H4N=NC6H4SO3)(4)center dot 2H(2)O}(n), has a linear chain structure composed of square-planar [Pt(en)(2)](2+) (en is ethylenediamine) and elongated octahedral trans-[PtCl2(en)(2)](2+) cations stacked alternately, bridged by Cl atoms, along the b axis. The Pt atoms are located on an inversion centre, while the Cl atoms are disordered over two sites and form a zigzag center dot center dot center dot Cl-Pt-IV-Cl center dot center dot center dot Pt-II center dot center dot center dot chain, with a Pt-IV-Cl bond length of 2.3140 (14) angstrom, an interatomic Pt-II center dot center dot center dot Cl distance of 3.5969 (15) angstrom and a Pt-IV-Cl center dot center dot center dot Pt-II angle of 170.66 (6)degrees. The structural parameter indicating the mixed-valence state of the Pt atom, expressed by delta = (Pt-IV-Cl)/(Pt-II center dot center dot center dot Cl), is 0.643.

      DOI: 10.1107/S2053229615019877

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      Other Link: http://orcid.org/0000-0003-1022-430X

    • Redetermination of the crystal structure of catena-poly[[[bis(ethylenediamine)platinum(II)]-μ-iodido-[bis(ethylenediamine)platinum(IV)]-μ-iodido] tetrakis(octane-1-sulfonate) dihydrate] Peer-reviewed

      Nobuyuki Matsushita

      Acta Crystallographica Section E: Crystallographic Communications71   1155 - 1158   2015

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:International Union of Crystallography  

      The structure of the title compound, which represents a mixed-valence platinum(II,IV) complex, {[PtIIPtIVI2(C2H8N2)4][CH3(CH2)7SO3]4·2H2O} n , has been redetermined in a different space group. In contrast to the previously reported determination in the space group P21 cn [Matsushita &amp
      Taira (1999). Synth. Met. 102, 1787-1788], the current model was refined in the centrosymmetric space group Pmcn using the original diffraction data. The title compound has a linear chain structure composed of square-planar [Pt(en)2]2+ and elongated octahedral trans-[PtI2(en)2]2+ cations (en is ethylenediamine) stacked alternately, bridged by the I atoms, parallel to the c axis. Inorganic layers aligned parallel to the bc plane, composed of the Pt-complex columns, the -SO3 - part of the octane-1-sulfonate anion, and the water molecule of crystallization, are stacked alternately with organic layers composed of the long-chain alkyl groups along the a axis. The Pt and I sites are located on the same mirror plane whereby the I site is equally disordered over two positions. The Pt and I atoms form a slight zigzag ⋯I - PtIV - I⋯PtII⋯ chain, with PtIV - I bond lengths of 2.6888(17) and 2.7239(17)Å, PtII⋯I contacts of 3.2065(17) and 3.1732(16)Å, and PtIV - I⋯PtII angles of 178.3(3) and 176.7(2)°. The mixed-valence state of the Pt site is expressed by the structural parameter δ = (PtIV - I)/(PtII⋯I), with values of 0.839 and 0.858 for the two independent I atoms. In the crystal, N - H⋯O hydrogen bonds involving the cationic chains, the sulfonate groups and water molecules of crystallization, stabilize the columnar structure.

      DOI: 10.1107/S2056989015016801

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      Other Link: http://orcid.org/0000-0003-1022-430X

    • Photochromic Property of Anionic Spiropyran with Sulfonate-substituted Indoline Moiety Peer-reviewed

      Akira Sugahara, Nara Tanaka, Atsushi Okazawa, Nobuyuld Matsushita, Norimichi Kojima

      CHEMISTRY LETTERS43 ( 3 ) 281 - 283   3 2014

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

      For fabricating photoresponsive multifunctional materials, we have developed the potassium salt of a new anionic spiropyran, 1',3',3'-trimethyl-6-nitrospiro [2H-1-benzopyran-2,2'-indoline]-5'-sulfonate (1(-)), with the sulfonate group present on the indoline moiety and whose crystal structure was revealed by single-crystal X-ray diffraction analysis. The photochromism of 1.K was demonstrated at room temperature in the KBr-diluted state, as well as in solution. The protonated spiropyran 1H shows negative photochromism.

      DOI: 10.1246/cl.130904

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      Other Link: http://orcid.org/0000-0003-1022-430X

    • Importance of spin-orbit coupling effect and solvent effect in electronic transition assignments of Pt-II complexes: In the case of cis/trans-[(PtCl2)-Cl-II(NH3)(2)] Peer-reviewed

      Hirotoshi Mori, Ryohei Kojima, Yuji Mochizuki, Waka Uenohara, Izumi Umezawa, Nobuyuki Matsushita

      JOURNAL OF MOLECULAR STRUCTURE1035   218 - 223   3 2013

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:ELSEVIER SCIENCE BV  

      Electronic excitation spectra of cis-platin (cis-[(PtCl2)-Cl-II(NH3)(2)]), which is a well-known antitumor drug, and trans-platin (trans-[(PtCl2)-Cl-II(NH3)(2)]) were experimentally observed and theoretically analyzed using ab initio spin-orbit CASPT2 (SO-CASPT2) calculations. Cis-platin showed two series of absorption bands in the wavelength regions of 250-350 nm and 350-450 nm. On the other hand, trans-platin showed three series of absorption bands in the wavelength regions of 260-280 nm, 300-340 nm and 360-400 nm. Comparing SO-CASPT2 calculations at the optimum structures in gas-phase conditions with those in DMF solvent, which were obtained by PCM implicit solvation model, it was clarified that both spin-orbit effect and solvent effect cannot be negligible even for quantitative assignments of electronic excitation spectra of cis/trans-platin. (c) 2012 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.molstruc.2012.11.027

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      Other Link: http://orcid.org/0000-0003-1022-430X

    • Excitation Photon Energy Dependence of the Relaxation Processes of the Photoexcited States in a Quasi-One-Dimensional Halogen Bridged Pt Complex Peer-reviewed

      Y. Wada, N. Matsushita, N. Ohashi

      SELECTED PAPERS FROM 17TH INTERNATIONAL CONFERENCE ON DYNAMICAL PROCESSES IN EXCITED STATES OF SOLIDS (DPC'10)13   66 - 69   2011

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      Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:ELSEVIER SCIENCE BV  

      Excitation photon energy dependence of the relaxation processes of the photoexcited states in a quasi-one-dimensional halogen-bridged platinum complex has been investigated by femto second transient absorption measurements. In a Pt complex, [Pt(en)(2)][Pt(en)(2)I-2](SO4)(2)center dot 6H(2)O (Pt-I-SO4), a photo-induced absorption (PA) band caused by self trapped excitons (STE's) has been observed when the excitation photon energy is close to the peak energy, 1.44eV, of the absorption band of the one photon allowed charge transfer (CT) exciton with odd parity. In addition, a long lived PA bands caused by charged solitons (CS's) has been observed. The intensity of these long lived CS absorption band shows quadratic excitation power dependence. This shows that CS's pairs are not generated from odd-CT-excitons but from the higher energy two photon excited states. When the excitation photon energy is close to a half of the of the even CT-exciton energy, 1.84eV, PA bands caused by STE's and CS's have been observed. These states are generated from the two photon excited even CT-excitons. When the excitation photon energy is much higher than the energy of the odd CT-exciton, PA bands caused by CS's and polarons have been observed. The intensities of these PA bands show linear excitation power dependences. Photo-generated free electron hole pairs are considered to relax into CS's and polarons. (C) 2011 Published by Elsevier B. V.

      DOI: 10.1016/j.phpro.2011.02.016

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    • Two-photon absorption spectra and optical nonlinearity in an MX-chain compound Peer-reviewed

      Yoshiki Wada, Nobuyuki Matsushita

      JOURNAL OF LUMINESCENCE128 ( 5-6 ) 1035 - 1037   5 2008

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      Two-photon absorption spectra of an MX-chain compound [Pt(en)(2)][Pt(en)(2)I-2[SO4)(2)- 6H(2)O have been measured. The two-photon absorption coefficient at the peak energy of the two-photon absorption band has been found to be 1.3 x 10(3) cm/GW. This value is two orders of magnitude larger than that predicted by the gap-dependent scaling law derived for conventional semiconductors and larger than the value that has been reported in polydiacetylenes. Electro-reflectance spectra have been measured and analyzed by a three-level model. The large two-photon absorption coefficient can be explained in the framework of the model. (C) 2007 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.jlumin.2007.11.045

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    • A luminescent nonlinear-chain tetracyanoplatinate(II) forming a charge-transfer complex with methyl viologen Peer-reviewed

      Daisuke Shiota, Nobuyuki Matsushita

      CHEMISTRY LETTERS37 ( 4 ) 398 - 399   4 2008

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      We display that a tetracyanoplatinate(II) forming a charge-transfer complex with methyl viologen dication in the crystal exhibits intense luminescence despite no direct Pt center dot center dot center dot Pt interaction.

      DOI: 10.1246/cl.2008.398

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    • Single crystal X-ray diffraction study of a mixed-valence gold compound, (Cs2AuAuCl6)-Au-I-Cl-III under high pressures up to 18 GPa: Pressure-induced phase transition coupled with gold valence transition Peer-reviewed

      Nobuyuki Matsushita, Hans Ahsbahs, Stefan S. Hafher, Norimichi Kojima

      JOURNAL OF SOLID STATE CHEMISTRY180 ( 4 ) 1353 - 1364   4 2007

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:ACADEMIC PRESS INC ELSEVIER SCIENCE  

      We performed the single-crystal X-ray diffraction study of a perovskite-type gold mixed-valence compound, (Cs2AuAuCl6)-Au-I-Cl-III, under high pressures up to 18 GPa by using a dianiond-anvil-cell with helium gas as Lin ideal hydrostatic press ure-transmitting medium. The lattice parameters and the variable atomic positional parameters were obtained with reasonable accuracy at various pressures. A structural phase transition at ca. 12.5GPa from I4/mmm to Pm3m was found. The lattice parameters a() and ca, denoted in the tetragonal cell setting, result in the relationship 2 (1/2)(10 = co. and the superstructure reflections h k I (I is odd), caused by the shift of the Cl ions from the midpoint of the An ions, disappeared at pressures above the phase transition. Both elongated [(AuCl6)-Cl-III] and compressed [(AuCl6)-Cl-I] octahedra in the low-pressure phase smoothly approach regular octahedra with increasing pressure. Above the structural phase transition at 12.5GPa, all the [AuCl6] Octahedra are crystallographically equivalent, which shows that the tetragonal-to-cubic phase transition accompanies the valence transition from the Au-I/Au-III mixed-valence state to the Au-II single-valence state. (C) 2007 Elsevier Inc. All rights reserved.

      DOI: 10.1016/j.jssc.2007.01.037

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    • Ultrahigh-pressure effects in metallo-organics Peer-reviewed

      Seiichi Kagoshima, Ryusuke Kondo, Nobuyuki Matsushita, Momoka Higa, Sergey V. Ovsyannikov, Nadezhda A. Shaydarova, Vladimir V. Shchennikov, Andrey Y. Manakov, Anna Y. Likhacheva

      PHYSICA STATUS SOLIDI B-BASIC SOLID STATE PHYSICS244 ( 1 ) 418 - 423   1 2007

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

      The results are reported of the pressure (P) dependence of the electrical resistance (R), the thermoelectric power (Seebeck effect) (S), and compressibility as well as the time dependence of R at fixed P up to 20 GPa for four metallo-organics based on the BEDT-TTF (bisethylenedithiolo-tetrathiofulvalene) group, theta-(BEDT-TTF)(2)CsZn(SCN)(4), alpha-(BEDT-TTF)(2)I-3, beta'-(BEDT-TTF)(2)PF6, and (BEDT-TTF)-TCNQ. X-ray powder and single-crystal diffraction studies were also made on theta-(BEDT-TTF)(2)CsZn(SCN)(4) at high pressures up to P similar to 10 GPa. The R values of all the crystals decreased with pressure up to P similar to 3-5 GPa (low-pressure regime), and then the sign of dR/dP inverted (high-pressure regime). From the investigation of the mechanical and structural properties, these materials were found to have a large compressibility in the low-pressure regime, and a small one in the high-pressure region. In theta-(BEDT-TTF)(2)CsZn(SCN)(4) we observed pressure-induced reversible degradation (amorphization) in structure without a solid-phase reaction. (C) 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

      DOI: 10.1002/pssb.200672530

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    • Crystalline polymorphism of bis[o-semibenzoquinonediimine(1-)]platinum(II) Peer-reviewed

      Yosuke Konno, Nobuyuki Matsushita

      BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN79 ( 8 ) 1237 - 1239   8 2006

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      A platinum complex with a non-innocent ligand, [Pt-II(L)(2)] (1), where L is o-semibenzoquinonediimine mono-anion, has two polymorphs. In one polymorph, molecules related by translation are arranged in the same orientation along the c axis, while in the other, molecules related by a c-glide plane are aligned alternately in different orientation.

      DOI: 10.1246/bcsj.79.1237

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    • pH-dependent color-change behavior of bis(o-phenylenediamine)platinum(II) complex and pH-dependent redox of bis(o-semibenzoquinonediimine)platinum(II) complex Peer-reviewed

      Yosuke Konno, Nobuyuki Matsushita

      BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN79 ( 7 ) 1046 - 1053   7 2006

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      pH-Dependent color changes of an innocent diamineplatinum(II) complex, [Pt(H2L)(2)]Cl-2 ([1]Cl-2)), where H2L is o-phenylenediamine, and the pH-dependent redox of non-innocent diimineplatinum(II) complexes, [Pt(L)21 (2) and [[Pt(L)(2)}(2)]Cl-2 ([2(2)]Cl-2), where L is o-semibenzoquinonediimine monoanion or neutral o-benzoquinonediimine, have been investigated by vis-NIR spectroscopy and cyclic voltammetry in solutions of various pH. The crystals of [1]Cl-2. 2H(2)O and [2(2)]Cl-2.6H(2)O have also been characterized by X-ray crystallography. [1]Cl-2 in an aqueous solution changes from colorless either to purple or to yellow-green depending on the pH of the solution. The purple solution gave a neutral complex 2 and the yellow-green solution yielded [2(2)]Cl-2.6H(2)O. In the latter complex, the monocation, [2](+), dimerizes forming a weak Pt-Pt bond [3.0109(4) angstrom] with no bridging ligands. The spectroscopy of [1]Cl-2 in the buffer solutions shows that the complex 2 is formed in the range of pH 4.6-5.8, while the complex [2](+) is generated in the range of pH 2.1-4.5. These results indicate that the one-electron redox process of [2](+)/2 depends on the pH of the solution. By adjusting the pH of the solution by adding acid or base, it is possible to reversibly control this redox process. This behavior is a kind of pH-dependent chromism because of their color being different.

      DOI: 10.1246/bcsj.79.1046

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    • A one-dimensional iodine-bridged Pt-II/Pt-IV mixed-valence complex, catena-poly[[[bis(ethylenediamine)-platinum(II)]-mu-iodo-[bis(ethylenedi- amine)platinum(IV)-mu-iodo] hydrogenphosphate dihydrogenphosphate iodide trihydrate] Peer-reviewed

      N Matsushita

      ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS62   M33 - M36   2 2006

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      The title compound, {[(PtPtI2)-Pt-II-I-IV(C2H8N2)(4)](HPO4)(H2PO4)I center dot 3H(2)O}(n), has a chain structure composed of square-planar [Pt(en)(2)](2+) and elongated octahedral trans-[PtI2(en)(2)](2+) cations (en is ethylenediamine) stacked alternately along the c axis and bridged by the I atoms; a three-dimensionally valence-ordered system exists with respect to the Pt sites. The title compound also has a unique cyclic tetramer structure composed of two hydrogenphosphate and two dihydrogenphosphate ions connected by strong hydrogen bonds [O center dot center dot center dot O = 2.522 (10), 2.567 (10) and 2.569 (11) angstrom]. The Pt and I atoms form a zigzag center dot center dot I-Pt-IV-I center dot center dot Pt(II)center dot center dot center dot chain, with Pt IV-I bond distances of 2.6997 (7) and 2.6921 (7) angstrom, interatomic Pt(II)center dot center dot center dot distances of 3.3239 (8) and 3.2902 (7) angstrom, and Pt-IV-I center dot center dot Pt-II angles of 154.52 (3) and 163.64 (3)degrees. The structural parameters indicating the mixed-valence state of platinum, expressed by delta = (Pt-IV-I)/(Pt-II-I), are 0.812 and 0.818 for the two independent I atoms.

      DOI: 10.1107/S0108270105041247

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    • Ultra high pressure application to organic conductors Peer-reviewed

      S. Kagoshima, R. Kondo, N. Matsushita, S. V. Ovsyannikov, N. A. Shaidarova, V. V. Shchennikov

      JOURNAL OF LOW TEMPERATURE PHYSICS142 ( 3-4 ) 409 - 412   2 2006

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      Under pressures as high as 20 GPa at room temperature the electronic and structural properties of organic conductors were measured to search for interesting pressure regimes where novel electronic states were expected. Thermopower, two-probe electrical resistance and contraction of sample's volume were measured on the organic conductors: theta-(BEDT-TTF)(2)CsZn(SCN)(4), alpha-(BEDT-TTF)(2)I-3, (BEDT-TTF)(2)PF6 and (BEDT-TTF)-TCNQ. All the materials exhibited a positive thermopower of the order of 10 mu V/K. At about 4-7 GPa (crossover pressure P-x) sharp changes were found in the pressure dependence of electronic and mechanical properties of all the substances under consideration related probably to the structural changes under pressure.

      DOI: 10.1007/s10909-006-9126-7

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    • Femtosecond transient absorption study of excitons in quasi-one-dimensional MX-chain compounds Peer-reviewed

      Y. Wada, N. Matsushita, Y. Konno, H. Haneda

      PHYSICA STATUS SOLIDI C - CURRENT TOPICS IN SOLID STATE PHYSICS, VOL 3, NO 103 ( 10 ) 3535 - +   2006

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      Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:WILEY-V C H VERLAG GMBH  

      Two photon absorption spectra of [Pt(en)(2)][Pt(en)(2)Br-2](SO4)(2)center dot 6H(2)O have been measured by the femtosecond transient absorption measurements. A two photon absorption band of an exciton with even parity has been found 0.8 eV above the one photon absorption band of an exciton with odd parity. The two photon absorption coefficient has been estimated at 1.5x10(2) cm/GW for pump energy of 1.56 eV and for probe energy of 1.95 eV at 100 K. (c) 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

      DOI: 10.1002/pssc.200672160

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    • A three-dimensional iodo-bridged mixed-valence gold(I,III) compound, Rb-2[(AuI2)-I-I][(AuI4)-I-III] Peer-reviewed

      N Matsushita, A Tanaka, N Kojima

      ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE61   I201 - I203   9 2005

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      Rb-2[(AuI2)-I-I][(AuI4)-I-III], dirubidium diiodoaurate(I) tetraiodoaurate(III), has a tilted and distorted perovskite-type structure which is isotypic with its bromide analogue Rb-2[(AuBr2)-Br-I][(AuBr4)-Br-III]. The structure contains compressed and elongated [AuI6] octahedra tilted away from each other and stacked alternately along the [001], [110] and [110] directions by sharing all the corner I- ions.

      DOI: 10.1107/S1600536805025432

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    • Redetermination of catena-poly[[[bis(ethylenediamine)platinum(II)]-mu-chloro-[bis(ethylenediamine)platinum(IV)]-mu-chloro]tetrakis-(hexafluorophosphate)] Peer-reviewed

      N Matsushita

      ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE61   M1301 - M1303   7 2005

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      The structure of the title compound, {[(PtCl)-Cl-II/IV-(C2H8N2)(2)](PF6)(2)}(n) or [Pt-II(C2H8N2)(2)][(PtCl2)-Cl-IV(C2H8N2)(2)]-(PF6)(4), has been redetermined [Matsushita (1993). Synth. Met. 56, 3401 - 3406] from image-plate data. No superstructure was observed, in contrast to the situation in related compounds. The linear chain structure consists of square-planar [Pt(en)(2)](2+) and elongated octahedral trans[PtCl2(en)(2)](2+) cations (en is ethylenediamine) stacked alternately, bridged by the Cl atoms, along the b axis. The Pt atom is located on an inversion centre and the Cl atom ( site symmetry 2) is disordered over two sites, resulting in Pt-IV-Cl and Pt-II.........Cl bond distances of 2.327 (4) and 3.191 (4) angstrom, respectively. The delta structural parameter, indicating the mixed-valence state of the Pt atoms, is 0.729.

      DOI: 10.1107/S1600536805017873

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    • A three-dimensional bromo-bridged mixed-valence gold(I,III) compound, (Cs2AuAuBr6)-Au-I-Br-III Peer-reviewed

      N Matsushita, F Fukuhara, N Kojima

      ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE61 ( 6 ) I123 - I125   6 2005

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      The title compound, dicaesium gold( I) gold(III) hexabromide or dicaesium dibromoaurate( I) tetrabromoaurate( III), Cs-2[(AuBr2)-Br-I][(AuBr4)-Br-III], has a distorted perovskite-type structure which is isotypic with its chloride and iodide analogues, (Cs2AuAuX6)-Au-I-X-III ( X is Cl or I). The structure contains compressed and elongated [AuBr6] octahedra stacked alternately along the [ 001] and [ 110] directions by sharing all the corner Br- ions. The compound is also characterized by the assembly of the gold complex ions [(AuBr2)-Br-I](-) and [(AuBr4)-Br-III](-). Structural parameters indicating the mixed-valence distortion of Au-I and Au-III due to displacement of two crystallographically independent halide ( X) ions from the mid-point between the two adjacent Au ions, expressed by (Au-X)/((AuX)-X-...), are 0.738 ( 2) along the c axis and 0.799 ( 1) in the ab plane. These values show that the mixed-valence distortion of the title bromide is intermediate between those of the chloride and the iodide. The distortion of the title bromide from the cubic system to the tetragonal system, expressed by 2(1/2) a/c = 0.9704 ( 1), is also intermediate between those of the chloride and the iodide.

      DOI: 10.1107/S1600536805016594

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    • A one-dimensional Cl-bridged Pt-II/Pt-IV mixed-valence complex catena-poly[[[bis(ethylenediamine)platinum(II)]-mu-chloro-[bis(ethylenediamine)- platinum(IV)]-mu-chloro] tetrakis(tetrafluoroborate)] Peer-reviewed

      N Matsushita

      ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE61   M514 - M516   3 2005

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      The title compound, {[Pt2Cl2(C2H8N2)(4)](BF4)(4)}(n) or [Pt-II(C2H8N2)(2)][(PtCl2)-Cl-IV(C2H8N2)(2)](BF4)(4), has a linear chain structure composed of square-planar [Pt(en)(2)](2+) and elongated octahedral trans- [PtCl2(en)(2)](2+) cations (en is ethylenediamine) stacked alternately, bridged by the Cl atoms, along the c axis. The Cl atom bridging the adjacent Pt atoms is disordered over two sites along the ... Cl-Pt-IV-Cl...Pt-II... chain, which lies on a twofold axis. The Pt-IV-Cl and Pt-II...Cl bond distances are 2.319 (3) and 3.052 (3) Angstrom, respectively. A structural parameter indicating the mixed-valence state of the Pt atom, expressed by delta = (Pt-IV-Cl)/(Pt-II...Cl), is 0.760.

      DOI: 10.1107/S1600536805004113

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    • Ultrafast dynamics of lattice relaxed states in quasi-one-dimensional MX-chain compounds Peer-reviewed

      Y Wada, N Matsushita, H Haneda

      JOURNAL OF LUMINESCENCE108 ( 1-4 ) 285 - 289   6 2004

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:ELSEVIER SCIENCE BV  

      Ultrafast relaxation processes of photoexcited states in a quasi-one-dimensional halogen-bridged mixed-valence metal complex [Pt(en)(2)][Pt(en)(2)I-2](SO4)(2).6H(2)O have been investigated by femtosecond transient absorption spectra measurements. A photoinduced absorption band caused by non-thermalized self-trapped excitons has been found. Oscillation of the absorption band caused by the symmetric Pt-I stretching mode of the self-trapped exciton with a frequency of 103 cm(-1) has been observed. The rise time of a polaron absorption band has been measured to be 1.2 ps. This corresponds to the decay time, 1.1 ps, of a photoinduced absorption band which oscillates with a frequency of 74 cm(-1). (C) 2004 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.jlumin.2004.01.061

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    • Crystal structure and structural transition caused by charge-transfer phase transition for iron mixed-valence complex (n-C3H7)(4)N[(FeFeIII)-Fe-II(dto)(3)] (dto = C2O2S2) Peer-reviewed

      M Itoi, A Taira, M Enomoto, N Matsushita, N Kojima, Y Kobayashi, K Asai, K Koyama, T Nakano, Y Uwatoko, J Yamaura

      SOLID STATE COMMUNICATIONS130 ( 6 ) 415 - 420   5 2004

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      (n-C3H7)(4)N[(FeFeIII)-Fe-II(dto)(3)] shows a new type of first order phase transition called chare-transfer phase transition around 120 K. where the charge transfer between Fe-II and Fe-III occurs reversibly. Recently, we have succeeded in obtaining single crystals of the title complex and determined the crystal Structure at room temperature. Crystal data: space group P6(3), a = 10.0618(5) Angstrom. c = 16.0424(7) Angstrom. V = 1406.54(12)Angstrom, Z = 2. Moreover. we have investigated the structural transition caused by the charge-transfer phase transition by means of powder X-ray diffraction measurement. When the temperature is decreased. the a-axis. which corresponds to the hexagonal ring size in two-dimensional honeycomb network structure of [Fe-II Fe-III(dto)(3)](infinity). contracts by 0.1 Angstrom at the charge-transfer transition temperature (T-CT) while the c-axis. perpendicular to the honeycomb network layer. elongates by 0.1 Angstrom at T-CT. Consequently, when the temperature is decreased, the unit cell volume decreases without noticeable anomaly around T-CT, which is responsible for the quite sniall vibrational contribution to the entropy change. compared with usual spin crossover transition. Thus, the charge-transfer phase transition around 120 K for (n-C3H7)(4)N[Fe-II Fe-III(dto)(3)] is regarded as spin entropy driven phase transition. (C) 2004 Elsevier Ltd. All rights reserved.

      DOI: 10.1016/j.ssc.2004.02.034

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    • A one-dimensional Cl-bridged Pt-II/IV mixed-valence complex, catena-poly[[bis(ethylenediamine)platinum(II)-mu-chloro-bis(ethylenediamine)-platinum(IV)-mu-chloro]tetrakis(hydrogensulfate)] Peer-reviewed

      N Matsushita

      ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE59   M26 - M28   1 2003

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

      The title compound, [PtCl2(C2H8N2)(4)](HSO4)(4) or [Pt(C2H8N2)(2)][Pt2Cl2(C2H8N2)(2)](HSO4)(4), has a linear chain structure composed of square-planar [Pt(en)(2)](2+) and elongated octahedral trans-[PtCl2(en)(2)](2+) cations (en is ethylenediamine) stacked alternately, bridged by the Cl atoms, along the c axis. The Cl atom bridging the adjacent Pt atoms is disordered over two sites along the...Cl-Pt-IV-Cl...Pt-II...chain, which lies on a twofold axis. The Pt-IV-Cl and Pt-II...Cl bond lengths are 2.323 (2) and 3.142 (2) Angstrom, respectively. A structural parameter delta=(Pt-IV-Cl)/(Pt-II...Cl), indicating the mixed-valence state of the Pt atom (delta=0.739), shows a good correlation with the data of the intervalence charge-transfer (IVCT) absorption band.

      DOI: 10.1107/S1600536802022584

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    • Single-crystalline photochromism of bis[2-(aminomethyl)pyridine]platinum(II) chloride monohydrate Peer-reviewed

      H Nishimura, N Matsushita

      CHEMISTRY LETTERS ( 9 ) 930 - 931   9 2002

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      Bis[2-(aminomethyl)pyridine]platinum(II) chloride monohydrate [Pt(amp)(2)]Cl-2.H2O has been found to exhibit photochromism in single-crystalline phase. Single crystals of the chloride were changed from almost colorless to pale-blue by the irradiation of the light. Its aqueous solution, however, shows no photochromic behavior. Absorption bands induced by the irradiation of the light show dichroism in the single crystals. The photochromic behavior of the present platinum complex chloride is very interesting, because it occurs in single-crystalline phase but not in solution.

      DOI: 10.1246/cl.2002.930

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    • Crystal structure and physical properties of BEDT-TTF (bis(ethylenedithio)tetrathiafulvalene) salt coupled with a photo-sensitive transition metal complex Peer-reviewed

      M Ohkubo, T Komatsu, N Matsushita, N Kojima, G Saito

      MOLECULAR CRYSTALS AND LIQUID CRYSTALS376   147 - 152   2002

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:TAYLOR & FRANCIS LTD  

      A new salt of BEDT-TTF with photo-sensitive transition metal complex [RuCl5(No)](2-) has been synthesized. The crystal structure was determined and attributed to the kappa-type salt. Although calculated band structure shows two dimensional Fermi surfaces and predicts a metallic behavior, the resistivity shows semiconducting temperature dependence up to 6 kbar. Both the ESR signals of BEDT-TTF+ and NO. exhibited a photo-induced effect.

      DOI: 10.1080/10587250210746

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    • Mixed-valence state of a one-dimensional platinum complex with a counter ion having two alkyl chains and its liquid crystal phase Peer-reviewed

      A Taira, N Matsushita

      MOLECULAR CRYSTALS AND LIQUID CRYSTALS379   297 - 302   2002

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:TAYLOR & FRANCIS LTD  

      We have investigated optical property and crystal structure of a one-dimensional halogen-bridged platinum complex (MX chain compound) with a counter ion having two alkyl chains, [Pt(en)(2)][PtCl2(en)(2)]{(CH3(CH2)(7)CO2)(2)CH2CHSO3}(4).2H(2)O, to elucidate influence of molecular fastener effect of the long alkyl chain on mixed-valence state of the platinum atoms. Thermal-behavior observations of the complex were also performed using a polarizing optical microscope without and with crossed nicols to examine thermal change of the mixed-valence state and appearance of the liquid crystal phase. Consequently, the complex has exhibited that the interaction between the platinum atoms is strengthened and the Pt-II-Pt-IV distance is shortened by doubling the number of alkyl chains around the platinum complex moieties compared with a corresponding PtCl chain complex with a single alkyl chain counter ion. We have also observed a texture of liquid crystal at about 200 degreesC.

      DOI: 10.1080/10587250290090633

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    • Ultrafast relaxation processes of solitons, polarons, and self-trapped excitons in MX-chain Peer-reviewed

      Y Wada, N Matsushita, A Taira, T Mitsuhashi

      JOURNAL OF LUMINESCENCE94   787 - 790   12 2001

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:ELSEVIER SCIENCE BV  

      Ultrafast relaxation processes of photoexcited states of a quasi-one-dimensional halogen-bridged mixed-valence metal complex [Pt(en)(2)][Pt(en)(2)Cl-2](PF6)(4) have been investigated by femtosecond transient absorption spectra measurements. It has been found that a considerable part of the neutral soliton pairs is generated directly from photogenerated charge transfer excitons. Charged soliton pairs have been found to be generated from free electron-hole pairs. The rise time and the decay time of the charged soliton absorption band are 2.2 and 6.5 ps, respectively. The polaron pairs are generated from free electron-hole pairs within time resolution. (C) 2001 Elsevier Science B.V. All rights reserved.

      DOI: 10.1016/S0022-2313(01)00369-6

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    • Ultrafast relaxation processes of the photoexcited states in MX-chains Peer-reviewed

      Y Wada, N Matsushita, T Mitsuhashi

      SYNTHETIC METALS120 ( 1-3 ) 1063 - 1064   3 2001

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      Femtosecond transient absorption spectra of a quasi-one-dimensional halogen-bridged mixed-valence metal complex [Pt(en)(2)]Pt(en)(2)Cl-2] (PF6)(4) have been measured. It has been found that the neutral solitons are generated from charge transfer excitons within the time resoution (300fsec). It is found that charged solitons are generated by the interband excitation. The rise time and decay time of the charged soliton absorption band are 2.2psec and 6.5psec respectively.

      DOI: 10.1016/S0379-6779(00)01237-6

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    • Transient absorption and luminescence studies of the relaxation processes of the photoexcited states in wide gap MX-chain compounds Peer-reviewed

      Y Wada, N Matsushita, A Taira, T Mitsuhashi

      SYNTHETIC METALS116 ( 1-3 ) 397 - 400   1 2001

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      Millisecond transient luminescence and absorption spectra of wide gap MX-chain compound, [Pd(en)(2)][Pt(en)(2)Br-2](ClO4)(4), have been measured. A delayed luminescence band has been found at 1.55 eV. The time evolution of the intensity of the luminescence is proportional to the first derivative of the intensity of the photoinduced polaron absorption. The delayed luminescence band is considered to be caused by the radiative recombination of the self-trapped excitons which are generated in the annihilation processes of the polarons. (C) 2001 Elsevier Science B.V. All rights reserved.

      DOI: 10.1016/S0379-6779(00)00445-8

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    • P-T phase diagram and Au valence state of the perovskite-type Au mixed-valence complexes M-2[(AuX2)-X-I][(AuX4)-X-III] (M = K, Rb, Cs; X = Cl, Br, I) Peer-reviewed

      N Kojima, N Matsushita

      COORDINATION CHEMISTRY REVIEWS198 ( 1 ) 251 - 263   3 2000

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      M-2[(AuX2)-X-I][(AuX4)-X-111] (M = K, Rb, Cs; X = Cl, Br, I) are perovskite-type gold mixed-valence complexes, In this review, we describe their structural P-T phase diagram, the pressure induced Au valence transition from the Au-I,Au- III state to the Au-II one, which is coupled with a structural phase transition. The metallic cubic phase appearing under high pressure and high temperature can be obtained as a metastable phase even at ambient pressure and room temperature. In the pressure region below the Au valence transition, Cs-2[(AuX2)-X-1][(AuX4)-X-III] (X = Cl, Br, I) show metallic behavior, which is attributed to the Au valence-fluctuation. (C) 2000 Elsevier Science S.A. All rights reserved.

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    • Spatial correlations in the valence of metal ions in Ni1-xPdx(chxn)(2)Br-3 Peer-reviewed

      Y Wakabayashi, N Wakabayashi, M Yamashita, T Manabe, N Matsushita

      JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN68 ( 12 ) 3948 - 3952   12 1999

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      X-ray scattering experiments have been performed on a quasi-one dimensional system, Ni1-xPdx(chxn)(2)Br-3, Strong diffuse scattering was observed for x &gt; 0.7; and it was interpreted as due to spatial inhomogeneity in the valence of metal ions. This inhomogeneity takes the form of CDW in which the metal ions within a chain have valences alternating between +2 and +4. Correlations in the valence sequence could he determined parallel as well as perpendicular to the chain direction. Pair correlation functions deduced from the measurements show the existence Of strong correlation between the positions of bridging Br ions and those of Br counter ions. It is concluded that the valence of metal ions for z &lt; 0.7 is +3. T2lese results are consistent with previous data on optical and magnetic measurements.

      DOI: 10.1143/JPSJ.68.3948

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    • Organic inorganic hybrids of MX chain Peer-reviewed

      N Matsushita, A Taira

      SYNTHETIC METALS102 ( 1-3 ) 1787 - 1788   6 1999

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      We have investigated organic/inorganic hybrids of MX chain in order to make a dynamical mixed-valence system as the first attempt. We have obtained the hybrids of the MX (PtCl, PtBr, PB) chains with organic sulfonate as a counter ion. They show deep red color for PtCl, greenish golden color for PtBr, cooper color for Ptl, strong dichroism and thin plate form. We've performed the X-ray crystal analysis of a Ptl chain of them, its having octanesulfonate ion as a counter ion. The result shows that the compound has a layered structure consisting of organic layers of long all;yl chains of the counter ion and inorganic layeres which include the one-dimensional structure, Pt-l.

      DOI: 10.1016/S0379-6779(98)01161-8

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    • Photo-induced and doping effects on the non-linear excitation in [PtX2(en)][PtX4(en)](X=Cl, Br, I) Peer-reviewed

      A Takano, T Komatsu, N Matsushita, N Kojima

      SYNTHETIC METALS103 ( 1-3 ) 2153 - 2153   6 1999

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      We have investigated the photo-induced and doping effects on the non-linear excitations (i.e. solitons and polarons) for the neutral MX chain system, [PtX2(en)][PtX4(en)](X=Cl, Br, I). From the analysis of the hyperfine structure of ESR signal in X=Cl salt, the photo-induced non-linear excitation is attributed to the neutral soliton. The iodine-doped X=Cl salt reveals a strong and broad ESR signal, whose intensity and g-value as a function of temperature suggest the existence of the dense non-linear excitations and the strong magnetic interaction between them.

      DOI: 10.1016/S0379-6779(98)00667-5

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    • X-ray and optical study on the PtCl chain structure in [Pt(en)(2)][Pt(en)(2)Cl-2](BF4)(4) Peer-reviewed

      Y Wakabayashi, N Wakabayashi, N Kuroda, M Nishida, N Matsushita

      JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN67 ( 1 ) 186 - 191   1 1998

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      X-ray diffraction and optical absorption measurements were carried out on single crystals of [Pt(en)(2)][Pt(en)(2)Cl-2] (BF4)(4) (en = etylenediamine). This compound has a quasi-one dimensional structure with alternating (II and IV) Pt valences along the c-axis. An orthorhombic to monoclinic structural phase transition occurs around 255 K and the charge-transfer absorption edge was found to have a sudden shift at the transition. X-ray diffuse scattering was observed around (0 0 2n + 1) reciprocal points. While optical spectra were affected by irradiating the sample with blue light, the X-ray diffraction intensity did not change either by irradiation or by varying the sample temperature. We attribute the diffuse scattering to solitons produced during crystal growth. From measurements of thermal diffuse scattering, limited information about the phonon dispersion relation was obtained.

      DOI: 10.1143/JPSJ.67.186

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    • Crystal Structure of Mixed-Valence Gold Compound, Cs2AuIAuIIICl6 up to 18 GPa Peer-reviewed

      N. Matsushita, H. Ahsbahs, S. S. Hafner, N. Kojima, N. Matsushita

      Review of High Pressure Science and Technology/Koatsuryoku No Kagaku To Gijutsu7   329 - 331   1998

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      We have performed the single crystal X-ray structure analysis of the three-dimensional halogen-bridged mixed-valence compound, Cs2AuIAuIIICl6 under high pressures up to 18 GPa. The high pressure apparatus used is a diamond-anvil-cell with helium gas as an inert and hydrostatic pressure-transmitting medium. The pressure dependence of the unit cell parameters indicates a structural phase transition from tetragonal to cubic at 12.5 GPa. The high pressure phase has a space group, Pm3m. [mixed-valence, Au complex, perovskite structure, structural phase transition, high pressure]. © 1998, The Japan Society of High Pressure Science and Technology. All rights reserved.

      DOI: 10.4131/jshpreview.7.329

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    • Pressure-induced structural phase transition of LaCrO3 Peer-reviewed

      T Hashimoto, N Matsushita, Y Murakami, N Kojima, K Yoshida, H Tagawa, M Dokiya, T Kikegawa

      SOLID STATE COMMUNICATIONS108 ( 9 ) 691 - 694   1998

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      Variation of crystal structure of LaCrO3 on pressure was investigated by X-ray diffraction for synchrotron radiation. X-ray diffraction pattern of LaCrO3 at room temperature under atmospheric pressure could be indexed assuming orthorhombic crystal symmetry. With the increase of pressure up to 5.4 GPa, structural phase transition was observed and crystal symmetry of LaCrO3 changed to hexagonal. The first order structural phase transition from orthorhombic to hexagonal is also observed under atmospheric pressure at 236 degrees C and variations of enthalpy, Delta H and molar volume, Delta V, at the phase transition were measured using differential scanning calorimetry and high temperature X-ray diffraction, respectively. By using Delta H, Delta V and Clapeyron formula, it was expected that the crystal phase transition occurred at room temperature under a pressure as low as 0.53 GPa. Presence of hexagonal phase in LaCrO3 under a pressure of 1.1-5.1 GPa showed agreement with the above thermodynamic expectation. (C) 1998 Elsevier Science Ltd. All rights reserved.

      DOI: 10.1016/S0038-1098(98)00446-3

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    • Decay kinetics of long-lived photogenerated kinks in an MX chain compound Peer-reviewed

      N Kuroda, Y Wakabayashi, M Nishida, N Wakabayashi, M Yamashita, N Matsushita

      PHYSICAL REVIEW LETTERS79 ( 13 ) 2510 - 2513   9 1997

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      The time evolution of the thermal bleaching of the long-lived, photogenerated midgap absorption band in a PtCl chain compound is examined in a temperature range 220-330 K. The long-lived absorption arises from kinks each confined in a segment of the PtCl chain by energy barriers of the order of 0.5 eV. Because of a random distribution of the barrier height the pair coalescence decay shows a ln t dependence at all temperatures in the experimental range, 0-60 min, of time t after discontinuation of laser pumping.

      DOI: 10.1103/PhysRevLett.79.2510

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    • A three-dimensional iodo-bridged mixed-valence gold(I,III) compound, Cs2Au(I)Au(III)I-6 Peer-reviewed

      N Matsushita, H Kitagawa, N Kojima

      ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS53   663 - 666   6 1997

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      The title compound, dicaesium gold(I) gold(III) hexaiodide, has a distorted perovskite structure. The crystal contains compressed and elongated [AuI6] octahedra stacked alternately along the [001] and [110] directions by sharing all the corner I atoms. The compound is also characterized by the assembly of the gold complex ions [(AuI2)-I-1](-) and [(AuI4)-I-III](-). The position of the two halogen atoms in (Cs2AuAuI6)-Au-I-I-III is closer to the midpoint between the two Au atoms than in (Cs2AuAuCl6)-Au-I-Cl-III. On the other hand, the distortion from the cubic system to the tetragonal system in the iodide is slightly larger than that in the chloride.

      DOI: 10.1107/S0108270197000279

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    • Phase transition and generation efficiency of mismatch of valence-alternation in the neutral MX chain system, [PtX(2)(en)][PtX(4)(en)] (X=Cl, Br, I) Peer-reviewed

      N Matsushita, A Takano, N Kojima

      MOLECULAR CRYSTALS AND LIQUID CRYSTALS SCIENCE AND TECHNOLOGY SECTION A-MOLECULAR CRYSTALS AND LIQUID CRYSTALS285   317 - 322   1996

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      We have investigated mid-gap absorption bands, their photo-induced absorption effect at various temperatures between liquid helium temperature and room temperature, and crystal structures between 150 K and 300 K in a neutral MX chain system, [PtX(2)(en)][PtX(4)(en)] (X=Cl, Br, I), which have one-dimensional structure, ...Pt-II...X-Pt-IV-X.... Temperature dependence of the intensity of the mid-gap absorption bands and the growth of the photo-induced absorption in [PtCl2(en)][PtCl4(en)] show that the generation efficiency of the mismatch of valence-alternation Is changed at 200-220 K. Temperature dependence of lattice parameters of [PtCl2(en)][PtCl4(en)] shows that the structural phase transition occurs at 220 K from the orthorhombic system to the monoclinic system by cooling. Comparison of the crystal structure between 195 K and 296 K shows that the basic structure does not change at the phase transition. The conformation of the chelate ring of the ethylenediamine is changed from the disordered state to the ordered state at the transition point by cooling. This result suggests that the order-disorder transition of the conformation of the ethylenediamine would be responsible for the generation efficiency of the mismatch of the valence alternation.

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    • Dependence of polaron, soliton, and self-trapped exciton relaxation on excitation photon energy in quasi-one-dimensional MX-complexes Peer-reviewed

      Y Wada, N Matsushita, J Tanaka, T Mitsuhashi

      JOURNAL OF LUMINESCENCE66-7 ( 1-6 ) 120 - 124   12 1995

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      The excitation energy dependence and time evolution of the photo-induced absorption (PA) spectra of [Pt(en)(2)][Pt(en)(2)Br-2](SO4)(2) . 6H(2)O have been investigated. Strong dependence of the PA-spectra on excitation photon energy has been found. This is explained by the photon-energy-dependent generation of polarons, neutral solitons, and a state (DG-state) which causes a pair of PA-bands. It is found that neutral solitons are efficiently generated from charge transfer excitons. On the other hand, polarons and DG-states are generated only from higher-energy excited states. It is also found that self-trapped excitons are most efficiently generated from the CT-excitons in the tail of the charge transfer exciton absorption band.

      DOI: 10.1016/0022-2313(95)00121-2

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    • COUNTERION RADIUS DEPENDENCE OF THE MIXED-VALENCE STATE IN MX CHAIN PLATINUM COMPLEXES Peer-reviewed

      N MATSUSHITA, H KITAGAWA, T MITANI

      SYNTHETIC METALS71 ( 1-3 ) 1933 - 1934   4 1995

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      We have investigated the size effect of the counter anion influencing to the mixed-valence state in MX chain platinum complexes. In order to study the counter-ion radius dependence of the mixed-valence state, we have measured the polarized reflectance spectra of [Pt(en)(2)][PtCl2(en)(2)]Y-4 (en=ethylenediamine, Y=PF6, HSO4, BF4) in single crystals, and analyzed the crystal structure of [Pt(en&gt;(2)][PtCl2(en)(2)](BF4)(4) by X-ray diffraction method. From comparing the tetrafluoroborate, the perchlorate, the hydrogensulfate and the hexafluorophosphate in the series of the chloro- bridged complex, we found that the mixed-valence gap of platinum decreases with decreasing the counter-anion radius.

      DOI: 10.1016/0379-6779(94)03113-K

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    • PRESSURE-DEPENDENCE OF THE MIDGAP ABSORPTION AND RAMAN-SCATTERING IN A NEW MX CHAIN COMPLEX [PT(EN)(2)][PT(EN)(2)CL-2](BF4)(4), (EN)=ETHYLENEDIAMINE Peer-reviewed

      N KURODA, M NISHIDA, N MATSUSHITA, M YAMASHITA

      SYNTHETIC METALS71 ( 1-3 ) 1921 - 1922   4 1995

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      Optical absorption and Raman scattering in the title substance are studied. An intragap absorption band at 1.67 eV is enhanced efficiently by the irradiation with 488.0 nm light even at room temperature. Under hydrostatic pressures, although a phase transition occurs at 0.6 GPa, this band follows the midpoint of the charge-transfer gap well. The Raman scattering by the Pt-Cl stretching mode shows that the original CDW phase coexists with the high-pressure CDW phase under pressures up to 3.0 GPa.

      DOI: 10.1016/0379-6779(94)03108-I

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    • ELECTRIC DICHROISM STUDIES ON ADSORPTION OF TRIS(5,5'-DIMETHYL-2,2'-BIPYRIDYL)RUTHENIUM(II) BY A COLLOIDALLY DISPERSED CLAY Peer-reviewed

      A YAMAGISHI, M TANIGUCHI, M TAKAHASHI, C ASADA, N MATSUSHITA, H SATO

      JOURNAL OF PHYSICAL CHEMISTRY98 ( 31 ) 7555 - 7561   8 1994

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      The adsorption of tris(5,5'-dimethyl-2,2'-bipyridyl)ruthenium(II) ([Ru(dmbpy)(3)](2+))) by a colloidally dispersed montmorillonite or saponite is studied by electric dichroism measurements. [Ru(dmbpy)(3)](2+) is adsorbed up to 100% of the cation-exchange capacity (CEC). An angle (theta) between the threefold symmetry (C-3) axis of a bound chelate and the direction normal to a clay surface is determined from the reduced linear dichroism extrapolated to the infinite field strength. At the loading level less than 13% of CEC, theta is determined to be 54-53 degrees and 57-62 degrees for montmorillonite and saponite, respectively. The results are contrasted with the bindings of [Ru(phen)(3)](2+) (phen = 1,10-phenanthroline) and [Ru(bpy)(3)](2+) (bpy = 2,2'-bipyridyl). These molecules orient the C-3 axes roughly in the perpendicular direction on a clay surface (theta = 16-18 degrees). When the amount of [Ru(dmbpy)(3)](2+) adsorbed is increased to 83%, and 77% of CEC for montmorillonite and saponite, theta decreases to 43-46 degrees and 50-53 degrees, respectively. The changes are ascribed to the intermolecular interactions among the bound molecules. Notably, a definite difference is observed in the dichroism spectra whether the metal complex is adsorbed as a pure enantiomer or a racemic mixture at the higher loading level. These results are compared with the theoretical predictions based on the Monte Carlo simulations.

      DOI: 10.1021/j100082a028

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    • EXCITATION PHOTON ENERGY-DEPENDENT RELAXATION PROCESSES OF THE PHOTOEXCITED STATES IN WIDE-GAP MX-CHAIN COMPLEXES Peer-reviewed

      Y WADA, N MATSUSHITA, M YAMASHITA

      MOLECULAR CRYSTALS AND LIQUID CRYSTALS SCIENCE AND TECHNOLOGY SECTION A-MOLECULAR CRYSTALS AND LIQUID CRYSTALS256   891 - 896   1994

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      Photo-induced absorption (PA) spectra of [Pt(en)(2)][Pt(en)(2)X(2)] (SO2)(2).6H(2)O (X=Cl and Br) have been measured. Large excitation photon energy dependent changes were found in the features of the PA spectra. The excitation photon energy dependences are considered to be due to the difference between the relaxation processes of the charge transfer excitons and those of the higher energy excited states. Several new PA bands have been found.

      DOI: 10.1080/10587259408039343

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    • OPTICAL STUDIES OF MX CHAIN COMPLEX [PT(EN)(2)][PTBR2(EN)(2)](SO4)(2)CENTER-DOT-6H(2)O UNDER HIGH-PRESSURE Peer-reviewed

      N MATSUSHITA, N KURODA

      MOLECULAR CRYSTALS AND LIQUID CRYSTALS SCIENCE AND TECHNOLOGY SECTION A-MOLECULAR CRYSTALS AND LIQUID CRYSTALS256   867 - 872   1994

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      We have measured the absorption and resonance Raman spectra in single crystals of the MX chain complex [Pt(en)(2)][PtBr2(en)(2)](SO4)(2) . 6H(2)O in order to study the mixed-valence state, the midgap state and the phase transition under various hydrostatic pressures up to 3.7 GPa at room temperature. Red shifts of both the intervalence charge-transfer absorption edge and the Pt-Br stretching mode Raman peak with increasing pressure show that the electronic state of Pt-II and Pt-IV in the mixed-valence state approaches that of Pt-III. An absorption band appearing above 2.5 GPa and a Raman peak appearing above 1.6 GPa suggest that a new phase coexists at pressures above 1.6 or 2.5 GPa. On the other hand, no enhancement of the optical absorption in the region of the midgap absorption bands (A-, B- and C-bands) is observed. This result shows that the midgap state is not generated by applying pressure at room temperature.

      DOI: 10.1080/10587259408039339

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    • CONTROLLING THE MIXED-VALENCE STATE OF HALOGEN-BRIDGED ONE-DIMENSIONAL PLATINUM COMPLEXES BY THE SUBSTITUTION OF COUNTER IONS Peer-reviewed

      N MATSUSHITA

      SYNTHETIC METALS56 ( 2-3 ) 3401 - 3406   4 1993

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      The mixed-valence states of halogen-bridged one dimensional platinum complexes have been investigated by the substitution of counter ions. The crystal structures of [Pt(en)2][PtCl2(en)2](PF6)4 (Cl-PF6), [Pt(en)2][PtCl2(en)2](HSO4)4 (Cl-HSO4) and [Pt(en)2][PtBr2(en)2](H2PO4)4.6H2O (Br-H2PO4) (en=ethylenediamine) have been determined by single-crystal X-ray diffraction, and their absorption edges have been measured at room temperature. The crystal data are: for Cl-PF6, monoclinic, P2/m, a=9.204(3), b=5.506(2), c=8.185(2)angstrom, 8=107.29(2)-degrees and Z=-1/2; for Cl-HSO4, orthorhombic, Ibam, a=9.261(l), b=14.422(2), c=10.929(1)angstrom, and Z=2; for Br-H2PO4, monoclinic, P2/a, a=19.463(2), b=5.722(l), c=8.325(1)angstrom, beta=101.59(l)-degrees and Z=1. The absorption edegs of the intervalence charge-transfer bands are c.a. 17,500cm-1 for Cl-PF6, c.a. 16,500cm-1 for Cl-HSO4 and c.a. 14,800cm-1 for Br-H2PO4. These results show that the counter ion size and the hydrogen atom of the counter ion influence the mixed-valence state. A mid-gap absorption band below the absorption edge is found at c.a. 14,700cm-1 in Cl-HSO4.

      DOI: 10.1016/0379-6779(93)90135-J

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    • PHOTO-GENERATION AND ANNIHILATION PROCESSES OF MID-GAP STATES IN QUASI-ONE-DIMENSIONAL HALOGEN-BRIDGED MIXED-VALENCE METAL-COMPLEXES Peer-reviewed

      Y WADA, N MATSUSHITA, M YAMASHITA

      SYNTHETIC METALS56 ( 2-3 ) 3395 - 3400   4 1993

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      Photo-generation and annihilation processes of the mid-gap states in quasi-one-dimensional halogen-bridged mixed-valence metal complexes (HMMC's) have been investigated by the excitation spectra measurements of photo-induced absorption (PA) bands and excitation power density dependence measurements of the PA bands. One kind of PA bands are efficiently generated from the CT-excitons. On the other hand, another kind of PA bands are efficiently generated from higher energy excited states. The generation efficiencies of the PA bands are proportional to the square root of the excitation light power density. This indicates that the mid-gap states which cause PA bands are mobile and are annihilated by the collision among them.

      DOI: 10.1016/0379-6779(93)90134-I

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    • STRUCTURE OF A ONE-DIMENSIONAL BR-BRIDGED PTII-PTIV MIXED-VALENCE COMPLEX, CATENA-POLY[BIS(ETHYLENEDIAMINE)PLATINUM(II,IV)-MU-BROMO BIS(HYDROGENSULFATE)] Peer-reviewed

      N MATSUSHITA, T TAGA, TSUJIKAWA, I

      ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS48   1936 - 1939   11 1992

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      [Pt(II)(C2H8N2)2][PtIVBr2(C2H8N2)2](HSO4)4, M(r) = 1178.65, orthorhombic, Ibam, a = 9.263 (2), b = 14.317 (3), c = 11.036 (5) angstrom, V = 1463.6 (8) angstrom3, Z = 2, D(x) = 2.67 Mg M-3, lambda(Mo Kalpha) = 0.71069 angstrom, mu = 12.64 mm-1, F(000) = 1116, T = 296K, R = 0.049, wR = 0.079 for 773 observed reflections [\F(o)\ &gt; 3sigma(\F(o)\)]. The crystal contains columns composed of square-planar [Pt(en)2]2+ and elongated octahedral trans-[PtBr2(en)2]2+ units (en = ethylenediamine) stacked alternately along the c axis. The Br ions bridging the adjacent Pt ions are disordered over two sites along the ... Br-Pt(IV)-Br...Pt(II)... linear chain. The Pt(IV)-Br and Pt(II)...Br bonds are 2.474 (3) and 3.044 (4) angstrom, respectively. The structural parameter delta = (Pt(IV)-Br)/(Pt(II)...Br) bears a good correlation with the data of the intervalence charge-transfer (IVCT) absorption edge (delta = 0.813). The hydrogen bonds along the column [N...0 = 3.06 (3) and 3.24 (2) angstrom] and the intercolumn hydrogen bonds [O...0 = 3.13 (3) angstrom] stabilize the structure.

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    • Design of hydrogen bond network in halogen-bridged mixed-valence platinum complexes by substitution of counter ion Peer-reviewed

      N. Matsushita, K. Toriumi, N. Kojima

      Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals216 ( 1 ) 201 - 206   1 6 1992

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      Sulfates in one-dimensional halogen-bridged mixed-valence platinum complexes were synthesized in order to elucidate contributions of hydrogen bonds between in-plane ligand amines and counter ions to the mixed-valence state. Their intervalence charge-transfer bands measured by using the single crystals and their structures determined by single crystal X-ray diffraction analyses show that the energy difference of dz2 orbitals between the PtII and the PtIV becomes larger with decreasing linkages between the Pt units by the hydrogen bonds, comparing with Perchlorates and hydrogensulfates. © 1992, Taylor &amp
      Francis Group, LLC. All rights reserved.

      DOI: 10.1080/10587259208028773

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    • Midgap absorption spectra in various kinds of halogen bridged mixed-valence Pt complexes Peer-reviewed

      Norimichi Kojima, Shinji Maeda, Nobuhisa Tanak, Nobuyuki Matsushita

      Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals216 ( 1 ) 163 - 168   1 6 1992

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

      We have investigated several kinds of midgap absorption spectra due to the mismatch of valence alternation(nonlinear excitations such as solitons and polarons) in various kinds of halogen bridged mixed-valence Pt complexes, [Pt(en)2][PtX2(en)2](SO4)2-6H2O(X=C1, Br and I), [PtX2(en)][PtX4(en)](X=C1 and Br), and [Pt(NH3)4][PtCl2(NH3)4](HSO4)4. Also we investigated the relationship between the stability of the mismatch of valence alternation and the crystal structure. © 1992, Taylor &amp
      Francis Group, LLC. All rights reserved.

      DOI: 10.1080/10587259208028767

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    • Relaxation processes of photoexcited states in halogen-bridged mixed-valence metal complexes

      Yoshiki Wada, Nobuyuki Matsushita, Masahiro Yamashita

      Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals216 ( 1 ) 175 - 180   1 6 1992

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

      Excitation spectra of the self-trapped exciton luminescence bands and those of photo-induced absorption bands of halogen-bridged mixed-valence metal complexes have been measured. The excitation spectra of luminescence bands begin to decrease from energies smaller than the peak energies of the charge transfer exciton absorption bands. The excitation spectra of photo-induced absorption bands begin to rise from the same energies. These show the competition between the self-trapped excitons and the photo-induced defect states in their generation processes. © 1992, Taylor &amp
      Francis Group, LLC. All rights reserved.

      DOI: 10.1080/10587259208028769

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    • DESIGN OF HYDROGEN-BOND NETWORK IN HALOGEN-BRIDGED MIXED-VALENCE PLATINUM COMPLEXES BY SUBSTITUTION OF COUNTER ION Peer-reviewed

      N MATSUSHITA, K TORIUMI, N KOJIMA

      MOLECULAR CRYSTALS AND LIQUID CRYSTALS216-18   201 - 206   1992

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:TAYLOR & FRANCIS LTD  

      DOI: 10.1080/10587259208028773

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      Other Link: http://orcid.org/0000-0003-1022-430X

    • MIDGAP ABSORPTION-SPECTRA IN VARIOUS KINDS OF HALOGEN BRIDGED MIXED-VALENCE PT COMPLEXES Peer-reviewed

      N KOJIMA, S MAEDA, N TANAKA, N MATSUSHITA

      MOLECULAR CRYSTALS AND LIQUID CRYSTALS216-18   163 - 168   1992

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:TAYLOR & FRANCIS LTD  

      DOI: 10.1080/10587259208028767

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      Other Link: http://orcid.org/0000-0003-1022-430X

    • RELAXATION PROCESSES OF PHOTOEXCITED STATES IN HALOGEN-BRIDGED MIXED-VALENCE METAL-COMPLEXES Peer-reviewed

      Y WADA, N MATSUSHITA, M YAMASHITA

      MOLECULAR CRYSTALS AND LIQUID CRYSTALS216-18   175 - 180   1992

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:TAYLOR & FRANCIS LTD  

      DOI: 10.1080/10587259208028769

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      Other Link: http://orcid.org/0000-0003-1022-430X

    • STUDIES OF MIXED-VALENCE STATES IN 3-DIMENSIONAL HALOGEN-BRIDGED GOLD COMPOUNDS, CS2AUIAUIIIX6 (X = CL, BR OR I) .1. SYNTHESIS, X-RAY-POWDER DIFFRACTION, AND ELECTRON-SPIN-RESONANCE STUDIES OF CSAU0.6BR2.6 Peer-reviewed

      H KITAGAWA, N KOJIMA, N MATSUSHITA, F BAN, TSUJIKAWA, I

      JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ( 11 ) 3115 - 3119   11 1991

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

      A new non-stoichiometric mixed-valence compound CsAu0.6Br2.6 has been prepared, and its powder X-ray diffraction profile, ESR spectra, and electrical conductivity determined. From its empirical formula the average valence of Au is +2.67. Powder diffraction data indicate that the compound has a cubic perovskite structure [cubic lattice, space group Pm3m, a = 5.462(2) angstrom]. This means that the AuBr6 octahedra are crystallographically equivalent. ESR measurements show the existence of a +II formal oxidation state for Au. The conductivity is four orders of magnitude higher than that of the Au(I)-Au(III) mixed-valence compound Cs2Au2Br6.

      DOI: 10.1039/DT9910003115

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      Other Link: http://orcid.org/0000-0003-1022-430X

    • Studies of mixed-valence states in three-dimensional halogen-bridged gold compounds, Cs2AuIAuIIIX6 (X = Cl, Br or I). Part 1. Synthesis, X-ray powder diffraction, and electron spin resonance studies of CsAu0.6Br2.6 Peer-reviewed

      Hiroshi Kitagawa, Norimichi Kojima, Nobuyuki Matsushita, Toshiro Ban, Ikuji Tsujikawa

      Journal of the Chemical Society, Dalton Transactions ( 11 ) 3115 - 3119   1991

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

      A new non-stoichiometric mixed-valence compound CsAu0.6Br2.6 has been prepared, and its powder X-ray diffraction profile, ESR spectra, and electrical conductivity determined. From its empirical formula the average valence of Au is + 2.67. Powder diffraction data indicate that the compound has a cubic perovskite structure [cubic lattice, space group Pm3m, a = 5.462(2) Å]. This means that the AuBr6 octahedra are crystallographically equivalent. ESR measurements show the existence of a +II formal oxidation state for Au. The conductivity is four orders of magnitude higher than that of the AuI-AuIII mixed-valence compound Cs2Au2Br6.

      DOI: 10.1039/DT9910003115

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    • STUDY OF MIXED-VALENCE STATE IN HALOGEN-BRIDGED MIXED-VALENCE PLATINUM(II,IV) COMPLEXES BY TEMPERATURE-DEPENDENCE OF INTERVALENCE CHARGE-TRANSFER SPECTRA Peer-reviewed

      N MATSUSHITA, N KOJIMA, T BAN, TSUJIKAWA, I

      BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN62 ( 12 ) 3906 - 3910   12 1989

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

      DOI: 10.1246/bcsj.62.3906

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    • 3 PHOTOINDUCED ABSORPTION-BANDS OF ONE-DIMENSIONAL HALOGEN-BRIDGED MIXED-VALENCE COMPLEX, [PT(EN)2][PTBR2(EN)2](SO4)2.6H2O Peer-reviewed

      N MATSUSHITA, N KOJIMA, N WATANABE, T BAN

      SOLID STATE COMMUNICATIONS71 ( 4 ) 253 - 258   7 1989

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:PERGAMON-ELSEVIER SCIENCE LTD  

      DOI: 10.1016/0038-1098(89)91009-0

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      Other Link: http://orcid.org/0000-0003-1022-430X

    • COMPARISON BETWEEN OPTICAL-PROPERTIES OF SULFATES AND HYDROGEN SULFATES IN HALOGEN-BRIDGED MIXED-VALENCE PLATINUM(II,IV) COMPLEXES Peer-reviewed

      N MATSUSHITA, N KOJIMA, T BAN, TSUJIKAWA, I

      BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN62 ( 6 ) 1785 - 1790   6 1989

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

      DOI: 10.1246/bcsj.62.1785

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    • PHOTOINDUCED ABSORPTION-BAND IN ONE-DIMENSIONAL HALOGEN-BRIDGED MIXED-VALENCE PLATINUM COMPLEX - [PT(EN)2][PTI2(EN)2](SO4)2.6H2O AND ITS AU-DOPED COMPLEX - [AUXPT1-XI(EN)2]SO4.3H2O Peer-reviewed

      N MATSUSHITA, N KOJIMA, T BAN, TSUJIKAWA, I

      JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN56 ( 11 ) 3808 - 3811   11 1987

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:PHYSICAL SOCIETY JAPAN  

      DOI: 10.1143/JPSJ.56.3808

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    • STRUCTURES OF DIGUANIDINIUM TETRACHLOROPALLADATE(II) AND GUANIDINIUM TETRACHLOROAURATE(III) Peer-reviewed

      H KIRIYAMA, N MATSUSHITA, Y YAMAGATA

      ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS42   277 - 280   3 1986

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:MUNKSGAARD INT PUBL LTD  

      DOI: 10.1107/S010827018609649X

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    Misc.

    Books and Other Publications

    • フォトクロミズムの新展開と光メカニカル機能材料(普及版)

      入江正浩, 関隆広監修( Role: Contributor)

      シーエムシー出版  7 2018 

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    • 改訂 化学

      松下 信之( Role: Contributor)

      東京書籍  3 2018 

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      Language:Japanese Book type:Textbook, survey, introduction

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    • 改訂 化学基礎

      松下 信之( Role: Contributor)

      東京書籍  3 2017 

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      Language:Japanese Book type:Textbook, survey, introduction

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    • 日本の結晶学(II)−その輝かしい発展−

      松下 信之( Role: Contributor)

      日本結晶学会  7 2014 

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    • 基礎化学実験 第3版

      東京大学教養学部化学部会編( Role: Contributor)

      東京化学同人  10 2012  ( ISBN:9784807907953

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      Language:Japanese Book type:Textbook, survey, introduction

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    • 化学の基礎77講

      東京大学教養学部化学部会編( Role: Joint editor)

      東京大学出版会  9 2003  ( ISBN:4130625012

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    Presentations

    • Tetracyanidoplatinate(II) and tetracyanidopalladate(II) salts with viologens and their luminescent properties based on intermolecular charge-transfer interactions Invited International conference

      MATSUSHITA Nobuyuki

      The 2nd International Symposium on Coordination Ionic Compounds  7 12 2018 

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      Language:English   Presentation type:Oral presentation (invited, special)  

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    • プロトンを対イオンに含むヘキサシアニド鉄(II)酸塩の粉末中性子構造解析

      松下 信之

      日本結晶学会  11 11 2018 

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      Language:Japanese   Presentation type:Oral presentation (general)  

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    • プロトンを対イオンに含むヘキサシアニド鉄(II)酸ビピペリジニウム塩の中性子構造解析

      松下 信之

      有機結晶シンポジウム  28 10 2018 

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      Language:Japanese   Presentation type:Oral presentation (general)  

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    • Luminescent charge-transfer salts composed of tetracyanidometallate(II) and viologens International conference

      MATSUSHITA Nobuyuki

      The 43rd International Conference on Coordination Chemistry (ICCC2018)  3 8 2018 

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      Language:English   Presentation type:Oral presentation (general)  

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    • 金属錯体と有機アクセプターからなる電荷移動塩の結晶構造と発光特性 Invited

      松下 信之

      日本結晶学会年会  24 11 2017 

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      Language:Japanese   Presentation type:Oral presentation (invited, special)  

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    • 白金錯体の単結晶フォトクロミズム

      松下信之

      シンポジウム「中性子回折による物質構造研究の新展開」  23 3 2010  茨城県中性子利用促進研究会 生命物質構造解析研究会 分子間反応機構の解明分科会

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      Language:Japanese   Presentation type:Symposium, workshop panel (nominated)  

      Venue:東京工業大学キャンパスイノベーションセンター  

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    Professional Memberships

    Research Projects

    • 白金錯体におけるドメイン構造を示す単結晶フォトクロミズムの発現機構解明

      文部科学省  科学研究費助成事業 

      松下信之

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      4 2009 - 3 2011

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\4400000 ( Direct Cost: \4400000 )

      ドメイン構造を呈する単結晶フォトクロミズムを示す白金錯体について,その発現機構の解明を目指す.

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    • 白金錯体の結晶フォトクロミックシステムの構造論的解明

      文部科学省  科学研究費助成事業 

      松下信之

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      4 2008 - 3 2009

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\2400000 ( Direct Cost: \2400000 )

      単結晶フォトクロミズムを示す白金錯体について,構造論的にその発現機構解明を目指す.

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    • 2次元検出器型高圧専用単結晶X線回折装置の試作

      日本学術振興会  科学研究費助成事業 

      松下信之

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      4 2000 - 3 2003

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\40200000 ( Direct Cost: \37320000 、 Indirect Cost:\2880000 )

      高圧力下での結晶構造解析を行うため,ダイヤモンドアンビルセルを搭載したイメージングプレート検出器型のX線回折装置を試作する.

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    • 「自己組織型混合原子価金属錯体の液晶性」

      池谷科学技術振興財団  池谷科学技術振興財団・平成12年度研究助成 

      松下信之

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      4 2000 - 3 2001

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\1000000 ( Direct Cost: \1000000 )

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    • 高圧力を利用した金属錯体の光機能の探索

      岩谷直治記念財団  岩谷直治記念財団・第26回(平成11年度)科学技術研究助成 

      松下信之

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      4 2000 - 3 2001

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\2000000 ( Direct Cost: \2000000 )

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    • 高圧力を利用した金属錯体分子システムの新機能・物性の探索

      日本学術振興会  科学研究費助成事業 

      松下信之

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      4 1999 - 3 2001

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\3700000 ( Direct Cost: \3700000 )

      高圧力を摂動場として利用し配位子場を制御し,金属錯体にこれまで見られなかった機能や物性の発現を目指す.

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    • 長鎖アルキル基を利用した金属錯体積層構造の構築と機能発現

      文部科学省  科学研究費助成事業 

      松下信之

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      4 1998 - 3 1999

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\1200000 ( Direct Cost: \1200000 )

      一次元混合原子価白金錯体に長鎖アルキル基を導入し,分子ファスナー効果を利用して,混合原子価状態の制御を目指す.

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    • 一次元金属錯体による新規非線形光学材料の開拓と特性評価

      旭硝子財団  旭硝子財団 自然科学系奨励研究助成 

      松下信之

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      4 1995 - 3 1997

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\1900000 ( Direct Cost: \1900000 )

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    • 新規高分子金属錯体非線形光学材料の開拓と特性評価

      日産科学振興財団  日産科学振興財団 第21回日産学術研究助成 

      松下信之

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      4 1995 - 3 1996

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\1700000 ( Direct Cost: \1700000 )

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    • 結合交替一次元電子系金属錯体の開拓と新機能発現

      日本学術振興会  科学研究費助成事業 

      松下信之

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      4 1995 - 3 1996

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\1000000 ( Direct Cost: \1000000 )

      結合交替のある一次元軽金属錯体を構築し,その交替の不整合に起因する物性を発現する化合物群を開拓し,新機能の開発を目指す.

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    • 二次非線形光学能をもつ一次元混合原子価白金錯体の開拓

      日本学術振興会  科学研究費助成事業 

      松下信之

      More details

      4 1994 - 3 1995

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\900000 ( Direct Cost: \900000 )

      アキラルな一次元混合原子価白金錯体結晶を構築し,その巨大な吸収係数を利用した大きな二次の非線形光学効果を示す化合物群を開発する.

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    • 混合原子価白金錯体の非線形光学能の研究

      住友科学財団  住友科学財団 基礎科学研究助成 

      松下信之

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      10 1993 - 9 1994

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\2000000 ( Direct Cost: \2000000 )

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    • 一次元白金錯体における原子価交替の不整合におよぼす水素結合の効果

      日本学術振興会  科学研究費助成事業 

      松下信之

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      4 1991 - 3 1992

      Authorship:Principal investigator  Grant type:Competitive

      Grant amount:\900000 ( Direct Cost: \900000 )

      一次元白金錯体において現れる原子価交替の不整合に基づくミッドギャップ状態に対する結晶内の水素結合ネットワークの効果を調べる.

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