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Synthesis of Discrete Polynuclear Complexes and Units for Metal-Assembled Compounds

Research Project

Project/Area Number 10149106
Research Category

Grant-in-Aid for Scientific Research on Priority Areas (A)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionKyushu University

Principal Investigator

OKAWA Hisashi  Kyushu University Professor, 大学院・理学研究院, 教授 (00037219)

Co-Investigator(Kenkyū-buntansha) MASHIMA Kazushi  Osaka University, Associate Professor, 大学院・基礎工学研究科, 助教授 (70159143)
ISOBE Kiyoshi  Osaka City University, Professor, 理学部, 教授 (70101285)
KITAGAWA Susumu  Kyuto University, Professor, 大学院・工学研究科, 教授 (20140303)
OSHIO Hiroki  University of Tsukuba, Professor, 化学系, 教授 (60176865)
Project Period (FY) 1998 – 2001
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥69,900,000 (Direct Cost: ¥69,900,000)
Fiscal Year 2001: ¥17,000,000 (Direct Cost: ¥17,000,000)
Fiscal Year 2000: ¥17,500,000 (Direct Cost: ¥17,500,000)
Fiscal Year 1999: ¥19,000,000 (Direct Cost: ¥19,000,000)
Fiscal Year 1998: ¥16,400,000 (Direct Cost: ¥16,400,000)
Keywordsheteronuclear complex / molecular magnet / coordination polymer / metal cluster / compartmental ligand / single-molecule magnet / metal-metal bond / spin exchange / フェロ磁性体 / フェリ磁性体 / 合成ゼオライト / 多孔性個体 / 酸化物クラスター / 一次元錯体 / 多孔性固体 / 構造解析 / 金属ー金属結合 / 配位高分子 / 電子スプレー質量分析 / 金属多重結合
Research Abstract

1) Heterodinuclear metal complexes of various combinations of metal ions were prepared using compartmental ligands and their physicochemical properties and functions were examined. Extensive magnetic studies were made for the complexes to reveal the significance of the electronic structures in determining the nature of magnetic interaction.
2) Cyanide-bridged bimetallic compounds of various network structures were prepared and their magnetic nature was studied. Spontaneous magnetization occurs for 2-D and 3-D network compounds but not for 1-D compounds. [Mn(glya)]_3[Cr(CN)_6]_3 (glya=glycine amide) has a 3-D network based on a defective cubane structure and shows ferromagnetic ordering with Tc=71 K, that is the highest among molecular magnets so far structurally characterized.
3) A new class of cluster compounds, comprising of 。ニorgano-metallic。ヌ unit and metal oxide unit, were prepared and their properties were studied. They include 。ニdouble bookshelf。ヌ type, 。ニwindmill。ヌ type, 。ニtriple cubane。ヌ type etc. and unique reactivities were found for some of them.
4) Porous coordination polymers of various networks were designed by the combination of metal ions and an organic building ligand such as 4,4'-bipyridine. They function as a host for including quest molecules such as CH_4, CO_2, O_2 and N_2.
5) Construction of covalently-linked linear metal clusters was studied and linear M-Mo-Mo-M (M=Rh, Ir) clusters were obtained by the reaction of Mo_2(pyphos)_4 (pyphos=6-dipenylphosphino-pyridonate) with M(I) complexes. The terminal metal is reactive due to coordinative unsaturation and some unique reactions were developed.
6) Tetranuclear Fe(III) compounds of a cubane structure were prepared using tridentate alcoholic ligands and their magnetic properties were examined. The complex [Fe_4(sae)_4(MeOH)_4] (sae=salicylideneaminoethanolate) was found to be a single-molecule magnet based on various magnetic studies.

Report

(5 results)
  • 2002 Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • Research Products

    (62 results)

All Other

All Publications (62 results)

  • [Publications] Hisashi Okawa: "Structures and Magnetism of Trinuclear CuGdCu Complex Derived from 2,6-Di(acetoacetyl)pyridine"Inorg. Chem., Commun.. 6. 15-18 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Hisashi Okawa: "A Bimetallic Magnetic System Exhibiting Reversible Ferromagnetism/Metamagnetism Modulation"Bull. Chem. Soc. Jpn.. 75. 1693-1698 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Susumu Kitagawa: "A New Class of Cyclic Hexamer [Co_6L_6]^<24-> (H_2L=hexaaza-triphenylene hexacarboxylic acid)"Angw. Chem. Int. Ed.. 40. 3817-3819 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Kiyoshi Isobe: "Structure and Reactivity of Novel Parallel Thiosulfito (SSO_2-S, S') Rhodium Dinuclear Complex"J. Chem. Soc., Chem. Commun.. 1756-1757 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Kazushi Mashima: "Unique Axial Interaction of a Quadruply-bonded Cr(II)-Cr(II) with Two Pt(II) Atoms in the Linearly Aligned Pt-Cr-Cr-Pt"Bull. Chem. Soc. Jpn.. 74. 67-75 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Hiroki Oshio: "Experimental and Theoretical Studies on Fervomagnetically Coupled Metal Complexes with Imino Ntroxides"Inorganic Chemistry. 40. 5518-5525 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 大川尚士, 伊藤 翼: "集積型金属錯体の科学"化学同人. 268 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Shiga, M. Ohba and H. Okawa: "Structure and Magnetism of Trinuclear Cu(II)Gd(III)Cu(II) Complex derived from 2,6-Di-(acetoacetyl)pyridine"Inorg. Chem. Commun.. 6. 15-18 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Miyasato, M. Ohba, and H. Okawa: "Synthesis, Structure and Magnetic Property of a Tetranuclear Iron(III) Complexes of "Face-to-Face" Type"Bull. Chem. Soc. Jpn.. 76(No.5). 1009-1010 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Inoue, M. Ohba, and H. Okawa: "Heterodinuclear M^<II>Ni^<II> Macrocyclic Compartmental Ligand. Anomalous EPR of Cu^<II>Ni^<II> Complex"Bull. Chem. Soc. Jpn.. 75(No.1). 99-107 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Inoue, H. Imai M. Ohba, and H. Okawa: "A 3-D Ferrimagnet with a High Magnetic Transition Temperature (Tc) of 53 K"Angew. Chem. Int. Ed.. 40(No.22). 4242-4245 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Yonemura, M. Ohba, and H. Okawa: "Coordination-Position Isomeric M^<II>Cu^<II> and Cu^<II>M^<II> Complexes of Macrocyclic Ligands"Inorg. Chem.. 41(No.3). 582-589 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N. Usuki, M. Ohba, and H. Okawa: "Effect of Intersheet Interaction upon Magnetic Ordering in 2-D Bimetallic Assemblies"Mol. Cryst. Liq. Cryst.. 376. 59-64 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H. Okawa, and M. Ohba: "Structure and Magnetism of Cyanide-bridged Bimetallic Compounds : Design of Complex-based Magnetic Materials"Bull. Chem. Soc. Jpn.. 75(No.6). 1191-1203 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N. Usuki, M. Ohba, and H. Okawa: "A Bimetallic Magnetic System Exhibiting Reversible Ferromagnetism/Metamagnetism Modulation"Bull. Chem. Soc. Jpn.. 75(No.8). 1963-1968 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Abe, K. Matsufuji, M. Ohba, and H. Okawa: "Synthesis and Site Specificity of Heterodinuclear Complexes of A Phenol-based 'End-off' compartmental Ligand"Inorg. Chem.. 41(No.17). 4461-4467 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Hori, Y. Mitsuka, M. Ohba, and H. Okawa: "Heterodinuclear M^<II>Cu^<II> Complexes of A Constrained Macrocyclic Compartmental Ligand"Inorg. Chim. Acta. 337. 113-121 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] S. Noro, M. Kondo, S. Kitagawa, and M. Yamashita: "Framework Engineering by Anions and Porous Functionalities of Cu(II)/4,4'-bpy Coordination Polymers"J. Am. Chem. Soc.. 124. 2568-2583 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] S. Noro, S. Kitagawa, M. Kondo, and K. Seki: "New Methane Adsorbent of Porous Coordination Polymer"Angew. Chem. Int. Ed. Engl.. 39. 2081-2084 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Shiomi, H. Kitayama, I. Kinoshita, N. Koga, and K. Isobe: "Structure and Reactivity of a Novel Parallel Thiosulfito (SSO_2-S,S') Rhodium Dinuclear Complex"J. Chem. Soc. Chem. Commun.. 1396-1397 (2002)

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      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Kinoshita, I. Kinoshita, and K. Isobe: "Synthesis and X-Ray Analysis of Mn-Mo Mixed-metal Oxide Cluster of Cubic Framework"Chem. Lett.. 1342-1343 (2002)

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      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H. Oshio, M. Yamamoto, T. Ito, and S. Tero-Kuroda: "Experimental and Theoretical Studies on Ferromagnetically Coupled Metal Complexes with Imino Nitroxide"Inorg. Chem.. 40. 5518-5525 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H. Oshio, M. Yamamoto, N. Hoshino, and T. Ito: "Ferromagnetic Interaction in Metal Complexes with Imino Nitroxides"Polyhedron. 20. 1621-1625 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Nakamura, and K. Mashima: "'Supine' and 'Prone' Ligands : Geometrical Preference of Conjugated Diene, 1-Azadiene, and 1,4-Diazadiene Ligands on Half-metallocene Complexes"J. Organomet. Chem.. 621. 224-230 (2001)

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      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Nishino, K. Mashima, K. Tani, and A. Nakamura: "Theoretical Studies of Multiple Metal-metal Bonds between Divalent Mo Ions in Dimers"Bull. Chem. Soc. Jpn.. 7l. 99-112 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Hisashi Okawa: "Trinuclear CuMnCu Complex of An Oxamide/Dioxime Ligand and Extension to A Bimetallic Magnetic Compound"J. Chem. Soc., Dalton Trans.. 2001・1. 64-70 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Hisashi Okawa: "Tetranuclear Mixed-metal Cu_2M_2 Complexes Derived from A Phenol-based Macrocyclic Ligand"Inorganic Chemistry. 40・15. 3739-3744 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Susumu Kitagawa: "A New Class of Cyclic Hexamer |Co_6L_6|^<24-> (H_2L= hexaaza-triphenylene hexacarboxylic acid)"Angw. Chem. Int. Ed.. 40・20. 3817-3819 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Kiyoshi Isobe: "Cesium(I)-Mediated 3-D Suprastructure by One-Pot Organization of Hydrogen-Bonded Ni Complexes"Inorganic Chemistry. 40・22. 5476-5478 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Kazushi Mashima: "Unique Axial Interaction of a Quadruply-bonded Cr(II)-Cr(II) with Two Pt(II) Atoms in the Linearly Aligned Pt-Cr-Cr-Pt"Bull. Chem. Soc. Jpn.. 74・1. 67-75 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Hiroki Oshio: "Experimental and Theoretical Studies on Ferromagnetically Coupled Metal Complexes with Imino Ntroxides"Inorganic Chemistry. 40・22. 5518-5525 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 北川 進: "集積型金属錯体"講談社. 285 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] N.Fukita: "Trinuclear CuMCu Complexes of An Oxamide/dioxime Ligand and Extension To A bimetallic Magnetic Material"J.Chem.Soc.Dalton Trans. 2001・1. 64-70 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Yonemura: "A Mixed-metal Cu^<II>_2Ni^<II>_2 Complex Derived from A Phenol-based Heterotetranucleating Macrocyclic Ligand"J.Chem.Soc.,Chem.Commun.. 2000・9. 817-819 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Yonemura: "Macrocyclic Effects upon Isomeric Cu^<II>M^<II> and M^<II>Cu^<II> Cores Formation with Unsymmetric Phenol-Based Macrocyclic Ligands"Proc.Ind.Acad.Sci.. 112・3. 291-310 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Suzuki: "Bimetallic Dioxygen Complexes Derived from 'End-off' Compartmental Ligands"Coord.Chem.Rev.. 200-202. 105-129 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] N.Fukita: "Synthesis, Structure and Magnetism of New Bimetallic Assemblies, [Ni(chxn)_2]_3[M(CN)_6]_2・2H_2O"Mol.Cryst.Liq.Cryst.. 342. 217-224 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.Furutachi: "Dinuclear Co^<II>M^<II>(M=Pb or Co) Complexes Having A 'Co(salen)' Entity in A Macrocyclic Framework"J.Chem.Soc.,Dalton Trans.. 2000・16. 2761-2769 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Shinoura: "A Heteronuclear Co(I)Cu(I) Complex with Co(salen) in A Macrocyclic Framework. Oxygenation Studies in Comparison with Analogous Complexes"Inorg.Chem.. 39・20. 2761-2769 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Noro: "New Methane Adsorbent of Porous Coordination Polymer, [Cu(SiF_6)(4,4'-bipyridine)_2]_n "Angew.Chem.,Int.Ed.Engl.. 39・7. 2081-2084 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Kondo: "Microporous Materials constructed from the Interpenetrated Coordination Networks. Structures and Methane Adsorption Properties"Chem.Mater.. 2000・12. 1288-1299 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Kondo: "A New Self-Assembled Porphyrin-Silver(I) Network"Chem.Lett.. 2000・7. 818-819 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.K.Kabir: "Novel Layered Structures Constructed From Iron-Chloranilate Compounds"Coord.Chem.Rev.. 198. 157-190 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Kitano: "Lantern-type dinuclear Cr^<III>Pt^<II> and V^<IV>Pt^<II> complexes bridged by pyridine-2-thiolate : Synthesis and characterization"J.Chem.Soc.Dalton Trans.. 2000・9. 995-1000 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Oshiki: "Substituent Effect on Organotin Tp^* Compounds as the Tp^* Reagent for the Preparation of Mono Tp^* Complexes of Group 4b Metals"Bull.Chem.Soc.Jpn.. 73・8. 1735-1748 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Tanaka: "Unique Axial Interaction of a Quadruply-Bonded Cr(II)Cr(II)with Two Pt(II) Atoms in the Linearly Aligned PtCrCrPt"Bull.Chem.Soc.Jpn.. 74・9. 67-75 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Mashima: "1-Aza-1,3-butadiene Complexes of Tantalum : Synthesis and Alkylation of TaCl_2(η_5 -C_5Me_5)(1-aza-1,3-butadiene)"J.Organomet.Chem.. 593/594. 69-76 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.Shimomura: "Formation of μ_4-Se_2 Complex by the Oxidative Coupling of μ-SeH Complex : Double-site Atomic Inversion of the μ_4-Se_2 Complex"J.Organomet.Chem.. 611・2. 386-391 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Nishikawa: "Synthesis and X-Ray Analysis of Mn-Mo Mixed Metal Oxide Cluster with Cubic Framework"Chem.Lett.. 2000・8. 1342-1343 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Kitano: "Lantern-type Dinuclear Cr(III)Pt(II)and V(IV)Pt(II) Complexes Bridged by Pyridine-2-thiolate. Synthesis and Characterization"J.Chem.Soc.Dalton Trans.. 2000・9. 995-1000 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K. Manseki: "Template Syntheses and Properties of Copper(II)-Lanthanide(III)Complexes of Phenol-Based Symmetric and Unsymmetric Dinucleating Macrocycles"J. Coord. Chem.. 48・1. 1-13 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M. Ohba: "[Mn(en)]_3[Cr(CN)_6]_2・4H_2O : A Three-dimensional Dimetallic Ferrimagnet (Tc=69K)with A Defective Cubane Unit"Angew. Chem. Int. Ed.. 38・12. 1795-1798 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] L. K. Thompson: "Dinuclear and Tetranuclear Copper(II)Complexes with Bridging(N-N)Diazine Ligands : Variable Magnetic Topologies"J. Chem. Soc. Dalton Trans. 2000・1. 69-77 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] S. Noro: "Syntheses and Crystal Structures of Iron Co-ordination Polymers with 4,4'-bpy and 4,4'-Azopyridine(azpy).2-D Networks Supported by Hydrogen Bonding"J. Chem. Soc. Dalton Trans. 1999・10. 1569-1574 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M. Tadokoro: "Cation-Dependent Formation of Superstructures by One-Pot Self-Organization of Hydrogen-Bonded Nickel Complexes"Angew. Chem. Int. Ed.. 38・1. 95-98 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Mashima: "Novel Synthesis of Lanthanoid Complexes Starting from Metallic Lanthanoid Sources"J. Chem. Soc., Dalton Trans.. 1999・22. 3899-3907 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Nobuo Fukita: "Bimetallic Assemblies[Ni(L)_2]_3[Fe(CN)_6]X_2(L=en,tn;X=PF_6,ClO_4)with a 3-D Network Extended through Fe^<II>-CN-Ni^<II> Linkages" Inorganic Chemistry. 37・5. 842-848 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Masaaki Ohba: "Structure and Manegnetic Properties of One-Dimensional PPh_4[Ni(Pn)_<>][M(CN)_6]-H_2O(M=Fe,Cr,Co)Bimetallic Assemblies" Inorganic Chemistry. 37・13. 3349-3354 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Hitoshi Miyasaka: "Synthesis,Crystal and Network Structures,and Magnetic Properties of a Hybird Layered Compound:[K(18-cr)(2-PrOH)_2][{Mn(acacen)}_2{Fe(CN)_6}]" Inorganic Chemistry. 37・21. 146-147 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takanori Nishioka: "Rational Synthesis of Stable Channel-like Cavities with Methane Gas Adsorption Properties:[Cu_2(pzdc)_2(L)]n(pzdc=pyrazine-2,3-dicarboxylate;L=a pillar ligand)" Angew.Chem.Int.Ed.Engl.38・1. 143-147 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Yakanori Nishioka: "Formation and Dynamic Properties of Triangular Rhodium m3-Sulfido Complex,[Rh_3Op_3(μ_3-μ_2-C_2H_2)(μ_3-S)]^<2+>Including Acetylene Ligand Generated by the Coupling" Organometallics. 17・9. 1637-1639 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Kazushi Mashima: "Dative Pd(O)-Mo(II)Bond in Terametal System:Preparation,Characterization and Reactions of a Tetranuclear Pd(O)-Mo(II)-Mo(II)-Pd(O)Supported by Four 6-Diphenylphosphino-2-pyridonate" J.Amer.Chem.Soc.120・20. 12151-12152 (1998)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2018-03-28  

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