European Journal of Inorganic Chemistry

Cover image for Vol. 2013 Issue 10‐11

Special Issue: Polyoxometalates (Cluster Issue)

April 2013

Volume 2013, Issue 10-11

Pages 1556–1967

Issue edited by: Ulrich Kortz, Tianbo Liu

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Essay
    7. Inside Cover
    8. Back Cover
    9. Masthead
    10. Graphical Abstract
    11. News
    12. Further Masthead
    13. Microreviews
    14. Short Communications
    15. Full Papers
    1. You have free access to this content
      Interactions between Keggin Anions in Water: The Higher Their Charge, the Higher Their Condensation? A Simulation Study (Eur. J. Inorg. Chem. 10-11/2013)

      Alain Chaumont and Georges Wipff

      Article first published online: 26 MAR 2013 | DOI: 10.1002/ejic.201390042

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      The front cover picture shows (top left) a snapshot of a simulated box of water containing [AlW12O40]5– POM anions and their H3O+ counterions, forming local aggregates (zoomed). Indeed, the free energy profile ΔG(d) calculated as a function of the POM···POM distance in water (top right) displays a minimum for the “contact” like-anion pair, corresponding to a high density of bridging counterions (inset, left). POMs also adsorb at the aqueous interface with graphite (bottom). The background is an extended view of the solution. Details are discussed in the article by G. Wipff and A. Chaumont on p. 1835 ff.

  2. Cover Profile

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    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Essay
    7. Inside Cover
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    10. Graphical Abstract
    11. News
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    13. Microreviews
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      Interactions between Keggin Anions in Water: The Higher Their Charge, the Higher Their Condensation? A Simulation Study (page 1556)

      Alain Chaumont and Georges Wipff

      Article first published online: 26 MAR 2013 | DOI: 10.1002/ejic.201300146

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      These results provide clues for understanding the formation of highly complex systems with supramolecular organization...

      This and more about the story behind the cover research can be found on Cover Profile and about the research itself on p. 1835 ff.

  3. Editorial

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    4. Editorial
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      A Feast of Polyoxometalate Chemistry (pages 1557–1558)

      Karen Hindson

      Article first published online: 26 MAR 2013 | DOI: 10.1002/ejic.201300229

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      EurJIC comes to you with a double issue on polyoxometalates, which reflects the energy and prolific output of the polyoxometalate community. As Guest Editors, Ulrich Kortz and Tianbo Liu gave us unlimited time and expert knowledge to make this issue a treasure trove of polyoxometalate chemistry.

  4. Guest Editorial

    1. Top of page
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    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Essay
    7. Inside Cover
    8. Back Cover
    9. Masthead
    10. Graphical Abstract
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    13. Microreviews
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    1. The Best of Polyoxometalates (pages 1559–1560)

      Ulrich Kortz and Tianbo Liu

      Article first published online: 26 MAR 2013 | DOI: 10.1002/ejic.201300230

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      An overview of the papers in this cluster issue is presented.

      “...Guest Editors Ulrich Kortz and Tianbo Liu provide a glimpse into the highlights of the many achievements of Michael Pope, who has been the most influential chemist in the field of polyoxometalates...”

      Read more by the Guest Editors on p. 1559.

  5. Essay

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    1. History and Vision

      Happy Birthday Keggin Structure! (page 1561)

      Michael T. Pope

      Article first published online: 26 MAR 2013 | DOI: 10.1002/ejic.201300282

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      This Essay for EurJIC's cluster issue on polyoxometalate chemistry pays tribute to the Keggin structure and acknowledges its contribution to the development of the field. This area of research has come a long way since its slow beginning, and there is great potential that lies ahead.

  6. Inside Cover

    1. Top of page
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      Inside Cover Picture: Nematic Ion-Clustomesogens from Surfactant-Encapsulated Polyoxometalate Assemblies (Eur. J. Inorg. Chem. 10-11/2013)

      Bao Li, Jing Zhang, Shan Wang, Wen Li and Lixin Wu

      Article first published online: 26 MAR 2013 | DOI: 10.1002/ejic.201390043

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      The inside cover picture shows nematic liquid crystals based on T-shaped quaternary ammonium encapsulated polyoxometalate complexes. The structural characterizations suggest the presence of a delicate synergy between organic and inorganic components. In the complexes, the central polyoxometalate clusters serve as nanosized knots, which collect the mesogenic ammonium units in a lateral way through strong electrostatic interaction. The laterally attached mesogens restrain the complexes from packing in a tight style, leading to nematic organization. This work demonstrates that the orientation of the peripheral mesogens has a pivotal influence on the liquid crystal organization of the ionic complexes. Details are discussed in the article by W. Li et al. on p. 1869 ff The authors thank Mr. Liang Yue for his valuable input for the cover design.

  7. Back Cover

    1. Top of page
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    6. Essay
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    10. Graphical Abstract
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      A Polyoxometalate-Based Coordination Polymer with the Diamondoid Topology (Eur. J. Inorg. Chem. 10-11/2013)

      Susanna Mandic, Merinda R. Healey, Jan M. Gotthardt, Kerwyn G. Alley, Robert W. Gable, Chris Ritchie and Colette Boskovic

      Article first published online: 26 MAR 2013 | DOI: 10.1002/ejic.201390044

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      The back cover picture shows the aqueous assembly of a new coordination polymer from 4-connecting inorganic and organic building blocks. The coordination polymer exhibits a diamondoid topology in which the lanthanide-functionalized polyoxometalate and tetracarboxylate building blocks act as pseudotetrahedral nodes. Details are discussed in the article by C. Ritchie, C. Boskovic et al. on p. 1631 ff. Stuffpoint.com is acknowledged for supplying the background graphic.

  8. Masthead

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    1. Masthead: Eur. J. Inorg. Chem. 10-11/2013 (page 1565)

      Article first published online: 26 MAR 2013 | DOI: 10.1002/ejic.201390045

  9. Graphical Abstract

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    1. Graphical Abstract: Eur. J. Inorg. Chem. 10-11/2013 (pages 1566–1579)

      Article first published online: 26 MAR 2013 | DOI: 10.1002/ejic.201390046

  10. News

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  11. Further Masthead

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    1. Further Masthead: Eur. J. Inorg. Chem. 10-11/2013 (page 1583)

      Article first published online: 26 MAR 2013 | DOI: 10.1002/ejic.201390048

  12. Microreviews

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    1. Enzyme Inhibition

      Polyoxometalates as Versatile Enzyme Inhibitors (pages 1585–1594)

      Holger Stephan, Manja Kubeil, Franziska Emmerling and Christa E. Müller

      Article first published online: 10 DEC 2012 | DOI: 10.1002/ejic.201201224

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      Polyoxometalates (POMs) are metal cluster compounds with a broad range of pharmacological properties, including antidiabetic, antibacterial, antiprotozoal, antiviral and anticancer activities. The inhibition of enzymes, in particular those accessible from the extracellular space, may constitute an important biological mechanism of action of POMs.

    2. Model Studies on Ti-POMs

      Hydrogen Peroxide Activation over TiIV: What Have We Learned from Studies on Ti-Containing Polyoxometalates? (pages 1595–1605)

      Oxana A. Kholdeeva

      Article first published online: 4 FEB 2013 | DOI: 10.1002/ejic.201201396

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      This Microreview summarizes recent results of the model studies of Ti-containing polyoxometalates (Ti-POM), which allowed new insight into mechanisms of H2O2 activation over TiIV centers and determination of the crucial factors that favor heterolytic oxidation of alkenes to lead to the selective formation of epoxides.

    3. Dendritic Polyoxometalate Catalysts

      Dendritic Polyoxometalate Hybrids: Efficient and Recoverable Catalysts for Oxidation Reactions (pages 1606–1619)

      Sylvain Nlate and Claire Jahier

      Article first published online: 10 DEC 2012 | DOI: 10.1002/ejic.201201129

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      Dendritic polyoxometalate (DENDRI-POM) hybrids are efficient and recoverable catalysts for oxidation reactions, including enantioselective transformations with up to 37 % ee. Although these ee values are still not satisfactory for practical asymmetric synthesis, its represents the best enantioselectivity reported to date in the oxidation of organic substrates with DENDRI-POM hybrids.

    4. Polyoxometalates

      Sulfite Anions as Structure-Directing Templates for the Engineering of Modular Polyoxometalates (pages 1620–1630)

      Haralampos N. Miras, George I. Chilas, Leroy Cronin and Themistoklis A. Kabanos

      Article first published online: 4 DEC 2012 | DOI: 10.1002/ejic.201201065

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      We describe synthetic approaches to the generation of building block libraries of polyoxometalates for use in the construction of functional materials and architectures. This building-block principle has led to the discovery of new compounds with interesting catalytic, electronic and structural properties, whilst at the same time leading to the rational synthesis of complex POM architectures.

  13. Short Communications

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    1. POM-Based Coordination Polymers

      A Polyoxometalate-Based Coordination Polymer with the Diamondoid Topology (pages 1631–1634)

      Susanna Mandic, Merinda R. Healey, Jan M. Gotthardt, Kerwyn G. Alley, Robert W. Gable, Chris Ritchie and Colette Boskovic

      Article first published online: 2 NOV 2012 | DOI: 10.1002/ejic.201200999

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      The polyoxometalate-based 3D coordination polymer [ϵ-PMo12O37(OH)3{La(H2O)3}4(L)]·28H2O [H4L = tetrakis(4-carboxyphenyl)silane] was readily synthesized from two pseudotetrahedral building blocks and exhibits a diamondoid network topology.

    2. Polyoxometalate Mimicry

      {Ce10Mn8}: Cerium Analogues of the Decavanadate Archetype (pages 1635–1638)

      Iurie L. Malaestean, Arkady Ellern and Paul Kögerler

      Article first published online: 30 NOV 2012 | DOI: 10.1002/ejic.201201247

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      Controlled condensation and oxidation of manganese(II) and cerium(III) precursors in the presence of structure-directing ligands result in a sequence of coordination clusters with increasing oxide/metal ratio, which leads to a Mn-decorated decavanadate-type cerium(IV) oxide framework.

    3. POMs with Rare Linkages

      A Polyoxometalate Containing Circular {P5W30} Units and Cubic {Cu4} Clusters (pages 1639–1643)

      Ling Huang, Lin Cheng, Sa-Sa Wang, Wei-Hui Fang and Guo-Yu Yang

      Article first published online: 20 NOV 2012 | DOI: 10.1002/ejic.201201133

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      The reaction of {P5W30} and copper acetate results in a new 3D framework, in which the {P5W30} wheels join the {Cu4} clusters to form dimeric units that are further linked by Cu complex bridges to produce an extended structure.

    4. Metal Substitution in POMs

      Diiron(III)-Containing 23-Tungsto-2-Borate: First Evidence of 3d Metal Substitution in the {BW13} Framework (pages 1644–1648)

      Santiago Reinoso, Pablo Vitoria, Leire San Felices and Juan M. Gutiérrez-Zorrilla

      Article first published online: 20 DEC 2012 | DOI: 10.1002/ejic.201201196

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      [{FeIII(H2O)3}2(WO2)(HBW11O39)2]8–, the first 3d-metal-containing tungstoborate whose structure differs from that of a monosubstituted Keggin framework, illustrates the possibility of performing substitutions of tungsten by 3d metals in the capping positions of the 13-tungstoborate skeleton.

    5. Ru and Os Supramolecular Assemblies

      Hexagonal Supramolecular Assemblies Based on a RuII(DMSO)3- or OsII(DMSO)3-Capped {HW9O33} Isopolyanion with Potassium Cations as Linkers (pages 1649–1653)

      Delina Barats-Damatov, Linda J. W. Shimon and Ronny Neumann

      Article first published online: 18 SEP 2012 | DOI: 10.1002/ejic.201200953

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      {HW9O33} isopolyanions were capped by MII(DMSO)3 moieties (where M = Ru, Os), which were, in turn, linked by potassium cations to give polymer chains that were somewhat different for the Ru and Os analogues. For Ru, the 3D structures showed channels defined by six polymer chains with a diameter of ca. 8 Å, while for Os, two types of channels of ca. 5.5 Å were formed defined by three polymer chains.

    6. Organic–Inorganic Hybrid POMs

      Towards Nanoscopic Mn-Containing Hybrid Polyoxomolybdates: Synthesis, Structure, Magnetic Properties, and Solution Behavior of a {Mn6Mo10} Cluster (pages 1654–1658)

      Lei Zhang, Rodolphe Clérac, Camelia I. Onet, Colm Healy and Wolfgang Schmitt

      Article first published online: 19 DEC 2012 | DOI: 10.1002/ejic.201201177

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      A synthetic approach to a hexadecanuclear, Mn-containing, organic–inorganic hybrid polyoxomolybdate is described. Magnetic studies confirm the predominance of antiferromagnetic exchange coupling between the Mn spin centers. MALDI-MS analyses highlight the interesting fragmentation behavior of the hybrid, which involves a number of oligonuclear cluster species.

    7. Lanthanide-Containing POMs

      Highly Selective and Efficient Lewis Acid–Base Catalysts Based on Lanthanide-Containing Polyoxometalates for Oximation of Aldehydes and Ketones (pages 1659–1663)

      Shen Zhao, Lujiang Huang and Yu-Fei Song

      Article first published online: 20 SEP 2012 | DOI: 10.1002/ejic.201200901

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      Two lanthanide-containing polyoxometalates (POMs) have been developed as Lewis acid–base catalysts for highly selective and efficient oximation of various aldehydes and ketones under mild conditions.

    8. Polyoxometalates

      trans-Dinitrosyl-Substituted Hexamolybdate and Study of Its Controllable NO Release (pages 1664–1671)

      Jiangwei Zhang, Jian Hao, Rao Naumaan Nasim Khan, Jin Zhang and Yongge Wei

      Article first published online: 8 FEB 2013 | DOI: 10.1002/ejic.201201144

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      Through a highly selective reaction route, the trans-dinitrosyl-substituted polyoxometalate (POM) (NBu4)4[Mo6O17(≡NO)2]4– was synthesized, and its structure was elucidated by standard spectroscopy and single-crystal X-ray diffraction studies. Its controllable release of NO was confirmed. This is the first time that a POM has been used for the controlled generation of the therapeutic NO moiety.

  14. Full Papers

    1. Top of page
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    3. Cover Profile
    4. Editorial
    5. Guest Editorial
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    1. Four Members of the Sandwich-Type Polytungstophosphate Family Based on Pentalacunary [HPW7O28]8– Building Blocks (pages 1672–1680)

      Dongdi Zhang, Yanhui Zhang, Juan Zhao, Pengtao Ma, Jingping Wang and Jingyang Niu

      Article first published online: 6 DEC 2012 | DOI: 10.1002/ejic.201201089

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      Four new sandwich complexes were formed in which two [HPW7O28]8– lacunary Keggin clusters encapsulate a single transitional ion to give clusters with the general formula [MII(HPW7O28)2]14– (in which M = Co, Cd, and Mn). [FeIII(HPW7O28)2]13– was found to display moderately good electrocatalytic activity towards the reduction of nitrite.

    2. POM Architectures

      Trilacunary Keggin-Type POMs as Versatile Building Blocks for Lanthanoid Silicotungstates (pages 1681–1692)

      Lubin Ni, Bernhard Spingler, Stephen Weyeneth and Greta R. Patzke

      Article first published online: 19 DEC 2012 | DOI: 10.1002/ejic.201201186

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      The structure-directing potential of lanthanoid cations for controlling POM architectures is combined with the versatile {SiW9O34} precursor. Depending on the synthetic conditions, {SiW9O34} can be transformed into Keggin-type sandwich compounds or into 2D/3D arrangements of the open Wells–Dawson silicotungstate {Si2W18O66}. This amplifies the linker functions of mid-lanthanoid cations in POM design.

    3. Polyoxometalates

      Two Types of Polyoxometalates Based on Circular P8W48 Cluster Units and Different Inclusions of Tetralanthanide and Octamanganese Centers (pages 1693–1698)

      Ling Huang, Lin Cheng, Wei-Hui Fang, Sa-Sa Wang and Guo-Yu Yang

      Article first published online: 19 DEC 2012 | DOI: 10.1002/ejic.201201132

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      Four P8W48-based wheel-shaped polyoxometalates with lanthanide clusters or Mn ions incorporated have been synthesized under hydrothermal conditions. Two dimeric lanthanide clusters and eight Mn2+ ions are incorporated owing to the different ionic radii of the lanthanide and Mn2+ centers.

    4. Germanomolybdates

      Monolacunary Germanomolybdates Binding with Transition-Metal Ions (CoII, NiII, and MnII) in Aqueous Solution: Synthesis, Crystal Structures, and Magnetic Properties (pages 1699–1705)

      Na Wang, Fengyan Li, Yuchao Wang, Lin Xu, Keyu Cui and Bingbing Xu

      Article first published online: 25 JAN 2013 | DOI: 10.1002/ejic.201201137

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      Three unusual transition-metal-monosubstituted germanomolybdates have been synthesized by the reactions of transition-metal ions (Co2+, Ni2+, Mn2+) with H4[α-GeMo12O40]·14H2O in aqueous solution, isolated as the imidazole salts, and characterized by a variety of techniques.

    5. Heteropolyniobates

      Two Members of the {X4Nb16O56} Family (X = Ge, Si) Based on [(GeOH)2Ge2Nb16H2O54]12– and [K(GeOH)2Ge2Nb16H3O54]10– (pages 1706–1712)

      Xin Zhang, Shu-Xia Liu, Shu-Jun Li, Yu-Huan Gao, Xue-Na Wang, Qun Tang and Yi-Wei Liu

      Article first published online: 28 FEB 2013 | DOI: 10.1002/ejic.201201117

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      Two new GeIV-containing heteropolyniobates are constructed by a hydrothermal–conventional combination approach. Compound 1 is an isolated cluster and compound 2 exhibits the first 1D ladder-like Ge/Nb heteropolyniobate cluster with μ-K atoms bridging them into extended structures. The photoluminescence and electrochemical properties of both compounds are investigated.

    6. Organotin Tungstogermanates

      Tris(organotin)tungstogermanate, a Sandwich Organometallic Derivative of a Keggin-Type Polyoxometalate: Synthesis and DFT Study (pages 1713–1719)

      Huizhang Liu, Nuno A. G. Bandeira, Vitor Félix and Maria José Calhorda

      Article first published online: 7 FEB 2013 | DOI: 10.1002/ejic.201201385

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      The [(C6H5SnOH)3(α-GeW9O34)2]14– anion is the first polyoxometalate based on two Keggin ions that contain germanium, which are bridged by three phenyltin groups. The threefold symmetry is reflected in the arrangement of the three OH groups trans to the phenyl groups in the tin fragment engaged in hydrogen bonding in the plane between the Keggin ions.

    7. Polyoxometalates

      A Hexanuclear Cobalt(II) Cluster Incorporated in a Banana-Shaped Tungstovanadate: [(Co(OH2)Co2VW9O34)2(VW6O26)]17– (pages 1720–1725)

      Hongjin Lv, Jie Song, Yurii V. Geletii, Weiwei Guo, John Bacsa and Craig L. Hill

      Article first published online: 19 DEC 2012 | DOI: 10.1002/ejic.201201130

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      The hexacobalt tungstovanadate, Na17[(Co(OH2)Co2VW9O34)2(VW6O26)]·31H2O (1), has been prepared and characterized both in the solid state and in solution. It crystallizes in the monoclinic space group P21/c, and consists of two tri-CoII substituted B-α-[(Co(OH2)Co2VW9O39)] Keggin units bridged by one unique [VW6O16] fragment, leading to a banana-shaped structure with idealized C2ν symmetry.

    8. Sandwich-Like Polyoxothiometalates

      Synthesis, Structure, and Tungsten NMR Characterization of {SbW9O33}9–{Mo2O2S2}2+ Sandwich-Like Polyoxothiometalates (pages 1726–1730)

      Marie-Anne Pilette, Sébastien Floquet, Jérôme Marrot, Francis Sécheresse and Emmanuel Cadot

      Article first published online: 3 JAN 2013 | DOI: 10.1002/ejic.201201295

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      Two new hybrids resulting from the reaction of the {Mo2O2S2}2+ thiocation with the trivacant {SbW9O33}9– have been obtained and characterized in the solid state and in solution by 183W NMR spectroscopy.

    9. Polyoxometalates

      Assembly of a Pentagonal Polyoxomolybdate Building Block, [Mo6O21]6–, into Crystalline MoV Oxides (pages 1731–1736)

      Masahiro Sadakane, Keisuke Endo, Katsunori Kodato, Satoshi Ishikawa, Toru Murayama and Wataru Ueda

      Article first published online: 20 DEC 2012 | DOI: 10.1002/ejic.201201142

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      Building block assembly of a polyoxomolybdate to form crystalline orthorhombic and trigonal MoV oxides.

    10. Regioselective Double Organic Functionalization of Polyoxotungstates through Electrophilic Addition of Aromatic Isocyanates to [P2W17O61(SnR)]7– (pages 1737–1741)

      Kévin Micoine, Max Malacria, Emmanuel Lacôte, Serge Thorimbert and Bernold Hasenknopf

      Article first published online: 3 JAN 2013 | DOI: 10.1002/ejic.201201147

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      Step by step: The Dawson-type polyoxotungstate α2-[P2W17O61]10– can be functionalized firstly with an organotin moiety SnR and subsequently with an isocyanate ArNCO. Independent variations of the organic groups R and Ar are possible. Thus, this methodology shows the way for direct double functionalizations of polyoxometalates.

    11. Organoruthenium POMs

      Organoruthenium-Containing Heteropoly-23-Tungstate Family [{Ru(L)}2(α-XW11O39)2WO2]m– (L = benzene, p-cymene; X = GeIV, SiIV, m = 10; BIII, m = 12) (pages 1742–1747)

      Nadeen H. Nsouli, Elena V. Chubarova, Rami Al-Oweini, Bassem S. Bassil, Masahiro Sadakane and Ulrich Kortz

      Article first published online: 8 FEB 2013 | DOI: 10.1002/ejic.201201229

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      Six organoruthenium-containing heteropoly-23-tungstates [{Ru(L)}2(α-XW11O39)2WO2]m– (L = benzene, p-cymene; X = GeIV, SiIV, m = 10; X = BIII, m = 12) have been synthesized and characterized by X-ray diffraction, thermogravimetric analysis, IR spectroscopy, and solution electrochemistry.

    12. Polyoxometalates

      Synthesis and Characterization of a Soluble Vanadium-Containing Keggin Polyoxoniobate by ESI-MS and 51V NMR: (TMA)9[V3Nb12O42]·18H2O (pages 1748–1753)

      Jung-Ho Son, C. André Ohlin, Emma C. Larson, Ping Yu and William H. Casey

      Article first published online: 10 DEC 2012 | DOI: 10.1002/ejic.201201056

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      A tetramethylammonium salt of vanadium-bearing polyoxoniobate ion (TMA)9[V3Nb12O42] in the α-Keggin structure is described. The compound is very soluble in water and stable near neutral pH.

    13. Monomer and Dimer of Mono-titanium(IV)-Containing α-Keggin Polyoxometalates: Synthesis, Molecular Structures, and pH-Dependent Monomer–Dimer Interconversion in Solution (pages 1754–1761)

      Yusuke Matsuki, Yuki Mouri, Yoshitaka Sakai, Satoshi Matsunaga and Kenji Nomiya

      Article first published online: 23 JAN 2013 | DOI: 10.1002/ejic.201201290

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      The monomer (Et2NH2)5[α-PW11TiO40]·2H2O and μ-oxo dimer (Et2NH2)8[(α-PW11TiO39)2O]·6H2O of mono-titanium(IV)-containing α-Keggin polyoxometalates (POMs) were successfully prepared. The molecular structure of the dimeric polyoxoanion with a μ-oxo group in 2 has been determined for the first time. The monomer–dimer equilibrium in solution was clarified by pH-varied 31P NMR spectroscopy.

    14. Isopolyniobates in Aqueous Solution

      An 17O NMR Study of Hydrolyzed NbV in Weakly Acidic and Basic Aqueous Solutions (pages 1762–1771)

      Walter G. Klemperer and Keith A. Marek

      Article first published online: 3 JAN 2013 | DOI: 10.1002/ejic.201201231

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      17O NMR spectra of aqueous Nb10O286– were measured after addition of different amounts of base. Evidence was obtained for the formation of protonated Nb24O7224–, Nb7O229– and Nb6O198–. The relative amounts of the different species formed were strongly dependent upon the amount base added, the age of the basified solution, and the identity of base added.

    15. Polytungstates

      Tin-Mediated Route to Polytungstates of RhII and PdII (pages 1772–1779)

      Maxim N. Sokolov, Irina V. Kalinina, Eugenia V. Peresypkina, Nikolay K. Moroz, Dmitry Yu. Naumov and Vladimir P. Fedin

      Article first published online: 10 DEC 2012 | DOI: 10.1002/ejic.201201162

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      Polyoxotungstates of SnII, PdII, and RhII, Na8[H2SnW12O42]·nH2O, Na2K(H)[Pd(H2O)4][H2W12O48{Pd(H2O)3}2]·10H2O, and Na8[Rh2(H2O)2(W5O18)2]·nH2O, were obtained and characterized by X-ray analysis and solid-state 1H NMR spectroscopy.

    16. Cagelike Iron Polycations

      Computational and Experimental Characterization of a Cagelike Fe15 Polycation (pages 1780–1787)

      Yu Hou, Xikui Fang, Kideok D. Kwon, Louise J. Criscenti, Danae Davis, Tim Lambert and May Nyman

      Article first published online: 7 JAN 2013 | DOI: 10.1002/ejic.201201128

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      Iron polynuclear clusters have fascinating structures, magnetic properties, and bear strong structural resemblance to other discrete metal oxide clusters, as well as related synthetic and natural materials. Solvothermal synthesis has produced a Fe15 polynuclear cationic cluster that features trimer building blocks of the common Keggin cluster geometry, and square-pyramidal Fe–Cl caps.

    17. 3D Tungstate Polymers

      3D Coordination Polymer of [HW7O24]5– Stabilized by a Copper(II) Complex and Sodium Cations: Structure, Solid-State Stability, and Aqueous Solution Behavior (pages 1788–1792)

      Xin-Fang Wang, Jie Cao, Kun-Lin Huang, Yan-Qing Xu, Ying-Nan Chi and Chang-Wen Hu

      Article first published online: 29 OCT 2012 | DOI: 10.1002/ejic.201200810

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      Compound 1, the first example of a heptatungstate polymer, has been synthesized and exhibits good solid-state stability at room temperature. However, dissociation of [HW7O24]5– to [W6O19]2– in aqueous solution was observed by ESI-MS. This suggests that the coordination bonds around [HW7O24]5– play an important role in the isolation and stabilization of the heptatungstate polyanion.

    18. Structured Polyoxotungstates

      Monomeric, Dimeric Helical, and 1D Nickel Polyoxotungstates Structured by Carboxylate Derivatives (pages 1793–1798)

      Guillaume Rousseau, Eric Rivière, Anne Dolbecq, Jérôme Marrot, Olivier Oms and Pierre Mialane

      Article first published online: 29 NOV 2012 | DOI: 10.1002/ejic.201201012

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      The functionalization of the {SiW9Ni4} Keggin fragment by various carboxylates led to compounds exhibiting very different topologies. By using dicarboxylate adipato ligands, a unique molecular-helical polyoxometalate is obtained. With aromatic dicarboxylate p-phenylenediacetato linkers a 1D compound is formed. The magnetic properties of two of the characterized species were fully interpreted.

    19. Hybrid Diblock Copolymers

      Synthesis, Characterizations, and Morphological Studies of Polyoxometalate-Containing Rod–Coil Diblock Copolymers (pages 1799–1807)

      Sanjiban Chakraborty, Lu Jin, Yong Li, Yucong Liu, Tanmoy Dutta, Da-Ming Zhu, Xingzhong Yan, Andrew Keightley and Zhonghua Peng

      Article first published online: 7 JAN 2013 | DOI: 10.1002/ejic.201201127

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      Hybrid rod–coil diblock copolymers containing P3HT as the rod block and a POM-modified polystyryl-type coil block have been synthesized and shown to exhibit nanophase separation after thermal annealing.

    20. K-Linked Polyanion Chains

      Dipotassium Diaquadiphosphatooctaperoxotetramolybdate, [K2(P2O7){MoO(O2)2}2{MoO(O2)2(OH2)}2]2– – a One-Dimensional Double Chain Array of Polyanions Linked by Potassium Cations (pages 1808–1814)

      Koji Aoki, Keisuke Iwata, Takahiro Iwata and Masato Hashimoto

      Article first published online: 6 FEB 2013 | DOI: 10.1002/ejic.201201190

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      A dipotassium diphosphatooctaperoxotetramolybdate was isolated as a tetramethylammonium salt. The diphosphatomolybdate moieties are linked by potassium atoms to form an infinite anionic 1D double chain. The chains are linked to each other by hydrogen bonds to water molecules to form a 2D network.

    21. Heteropolytungstates

      Bisorganophosphonyl and -Organoarsenyl Derivatives of Heteropolytungstates as Hard Ligands for Early-Transition-Metal and Lanthanide Cations (pages 1815–1820)

      Richard Villanneau, Aïcha Ben Djamâa, Lise-Marie Chamoreau, Geoffrey Gontard and Anna Proust

      Article first published online: 4 JAN 2013 | DOI: 10.1002/ejic.201201257

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      The coordination properties of polyoxometalate (POM) hybrids that incorporate organophosphonyl or -arsenyl functions were studied toward cations from different families of the periodic table (La3+, Ca2+, V5+, Ti4+). The structures of all complexes were determined by single-crystal X-ray diffraction and showed evidence for the particular hardness of the coordination sites in these POM hybrids.

    22. 1D Poly-Keggin Chains

      Three Polymeric Polyoxometalate Compounds Based on Twisted Poly-Keggin Chains (pages 1821–1826)

      Yuan-hang Ren, Yi-chen Hu, Zu-ping Kong, Min Gu, Bin Yue and He-yong He

      Article first published online: 4 FEB 2013 | DOI: 10.1002/ejic.201201374

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      Three polymeric POM compounds with one-dimensional poly-Keggin chains were isolated under hydrothermal conditions. The polymers consist of low-valence Keggin units, which are joined through MoV–O–MoV bridges or W–O–Cu bridges. Twisted chains are formed due to the different orientation of Keggin units during aggregation.

    23. Crystal Engineering

      In Situ Recrystallization of Polyoxometalates: From 0D Architectures to 2D Inorganic–Organic Hybrids (pages 1827–1834)

      Xuan Liu, Haiyan An, Zhaofei Chen, Hua Zhang, Ying Hu, Guibo Zhu, Yurii V. Geletii and Craig L. Hill

      Article first published online: 26 FEB 2013 | DOI: 10.1002/ejic.201201272

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      0D hybrid compound 1 transforms into 2D hybrid architecture 2 in the mother liquor during recrystallization through crystal disassembly and reassembly.

    24. Keggin Anions in Water

      Interactions between Keggin Anions in Water: The Higher Their Charge, the Higher Their Condensation? A Simulation Study (pages 1835–1853)

      Alain Chaumont and Georges Wipff

      Article first published online: 29 OCT 2012 | DOI: 10.1002/ejic.201200883

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      In water, [AlW12O40]5– anions are shown to form dimers and oligomers by a higher amount than their less charged [PW12O40]3– or [SiW12O40]4– analogues. This counterintuitive feature is due to specific counterion condensation onto the most charged dimers. Microscopic insights into the effects of anion granularity, sign of the charge, concentration, counterions, and solvation are presented.

    25. Charge Density

      Determination of the Effective Charge Density of pH-Responsive Keplerate Polyoxometalate Clusters by Means of Agarose Gel Electrophoresis (pages 1854–1858)

      Joseph M. Pigga and Tianbo Liu

      Article first published online: 21 JAN 2013 | DOI: 10.1002/ejic.201201230

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      The effective charge densities of Keplerate macroanions in dilute aqueous solutions were determined from gel electrophoresis measurements, which provided direct, quantitative evidence of the counterion association behavior around macroions. A close connection between the surface charge density of {Mo72Fe30} and their assembled blackberry structure sizes was observed.

    26. Decavanadate Counterion

      Counterion Affects Interaction with Interfaces: The Antidiabetic Drugs Metformin and Decavanadate (pages 1859–1868)

      Aungkana Chatkon, Pabitra B. Chatterjee, Myles A. Sedgwick, Kenneth J. Haller and Debbie C. Crans

      Article first published online: 8 MAR 2013 | DOI: 10.1002/ejic.201201345

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      The metformium decavanadate salt was synthesized and found to be very soluble in the inhomogeneous environment of sodium bis(2-ethylhexyl)sulfosuccinate reverse micelles. By using IR spectroscopy, the decavanadate–metformium material was found to affect the water pool and water organization near the interface of the reverse micelles differently, even in the presence of large excess amounts of Na+.

    27. Polyoxometalate Assemblies

      Nematic Ion-Clustomesogens from Surfactant-Encapsulated Polyoxometalate Assemblies (pages 1869–1875)

      Bao Li, Jing Zhang, Shan Wang, Wen Li and Lixin Wu

      Article first published online: 9 NOV 2012 | DOI: 10.1002/ejic.201200983

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      Polyoxometalates are encapsulated by quaternary ammonium surfactants, and the resultant complexes self-assemble into nematic structures with thermal stimulus. We demonstrate that the laterally attached mesogenic units have a pivotal role in the liquid crystal structures.

    28. Lanthanide Complexes

      Early-Lanthanide Complexes with All-Inorganic Macrocyclic Polyoxovanadate Ligands (pages 1876–1881)

      Masaki Nishio, Shinnosuke Inami and Yoshihito Hayashi

      Article first published online: 29 JAN 2013 | DOI: 10.1002/ejic.201201435

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      Complexes [LnVnO3n](n–3)– (Ln = LaIII, n = 10; Ln = CeIII, n = 9 or 10; Ln = PrIII, n = 9) with all-inorganic crown ether type polyoxovanadate ligands were synthesized and characterized by single-crystal X-ray diffraction studies. Site exchange of the coordinated and uncoordinated VO4 units in the heteropolyoxometalate frameworks was observed through variable-temperature 51V NMR spectroscopic studies.

    29. Graphene–POM Hybrids

      First Examples of Hybrids Based on Graphene and a Ring-Shaped Macrocyclic Polyoxometalate: Synthesis, Characterization, and Properties (pages 1882–1889)

      Shiwen Li, Rongji Liu, Rosa Ngo Biboum, Bénédicte Lepoittevin, Guangjin Zhang, Anne Dolbecq, Pierre Mialane and Bineta Keita

      Article first published online: 10 DEC 2012 | DOI: 10.1002/ejic.201201218

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      We report the facile synthesis of the first hybrids based on graphene (G) and the macrocyclic polyoxometalate [H7P8W48O184]33– (P8W48) alone or assembled with a PIL. Both methods lead to the production of stable water-dispersible P8W48@G hybrids. The hybrids were fully characterized by various spectroscopic methods, microscopy, and electrochemistry.

    30. Lanthanopolyoxometalate Composites

      Luminescent Transparent Composite Films Based on Lanthanopolyoxometalates and Filmogenic Polysaccharides (pages 1890–1896)

      Ricardo J. B. Pinto, Carlos M. Granadeiro, Carmen S. R. Freire, Armando J. D. Silvestre, Carlos Pascoal Neto, Rute A. S. Ferreira, Luís D. Carlos, Ana M. V. Cavaleiro, Tito Trindade and Helena I. S. Nogueira

      Article first published online: 3 JAN 2013 | DOI: 10.1002/ejic.201201174

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      The incorporation of lanthanopolyoxometalates (LnPOMs) or LnPOM/silica core/shell nanoparticles into either a chitosan derivative (HTCC) or pullulan originates clear transparent films that show lanthanide emission under UV irradiation (the image shows a HTCC film with [Eu(W5O18)2]9– under 366 nm excitation).

    31. Spin-Frustrated POMs

      Electronic and Spin Structures of Polyoxometalate V15 from a First-Principles Non-Collinear Molecular-Magnetism Approach (pages 1897–1902)

      Volodymyr V. Maslyuk, Ingrid Mertig, Oleg V. Farberovich, Alex Tarantul and Boris Tsukerblat

      Article first published online: 7 JAN 2013 | DOI: 10.1002/ejic.201201202

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      Here we present the results of the first-principles calculations of the electronic structure of spin-frustrated V15 cluster with the use of a generalized density-functional scheme allowing for the non-collinear spin configurations.

    32. Single-Molecule Magnets

      The Use of Polyoxometalates in the Design of Layer-Like Hybrid Salts Containing Cationic Mn4 Single-Molecule Magnets (pages 1903–1909)

      Salvador Cardona-Serra, Juan Modesto Clemente-Juan, Eugenio Coronado, Carlos Martí-Gastaldo and Efrén Navarro-Moratalla

      Article first published online: 25 JAN 2013 | DOI: 10.1002/ejic.201201390

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      Polyoxometalates (POMs) permit the controlled organization of single-molecule-magnet (SMM) units within the layered architecture of hybrid ionic crystals. By taking Mn4 (complex cluster) as a case study, the use of POMs with different sizes and charges yields differently packed structures. The slow relaxation properties of the SMM component are strongly affected by the counteranion employed.

    33. Reduction of Polyoxometalates

      Tungsten Redox Waves in [XMW11O40]n– (X = P, Si, Al and M = W, Mo, V, Nb, Ti) Keggin Compounds – Effect of Localised/Delocalised Charges (pages 1910–1916)

      Pablo A. Aparicio, Josep M. Poblet and Xavier López

      Article first published online: 18 FEB 2013 | DOI: 10.1002/ejic.201201384

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      The oxidising power of Keggin tungstates, [XW12O40]n, is inversely proportional to the negative charge that they carry. DFT calculations generalise this well-known rule and the nature of the charge increase is also considered. Three cases are discussed: (i) addition of a delocalised “blue” electron, (ii) addenda atom replacement or (iii) heteroatom replacement.

    34. ϵ-Keggin Structures

      Catalytic Hydrolysis of Adenosine Triphosphate (ATP) by Antitumoral ϵ-Keggin Core Compound, [H2MoV12O28(OH)12(MoVIO3)4]6–, at pH 5 and 7.5 (pages 1917–1925)

      Eri Ishikawa and Toshihiro Yamase

      Article first published online: 16 JAN 2013 | DOI: 10.1002/ejic.201201164

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      The catalytic hydrolysis of adenosine triphosphate (ATP) [to adenosine diphosphate (ADP) and phosphate] at 40 °C by [Me3NH]6[H2MoV12O28(OH)12(MoVIO3)4]·2H2O (PM-17) as an important candidate for antitumor chemotherapy is investigated at pH 5 and 7.5 with the help of 31P NMR spectroscopy, electrospray ionization mass spectrometry, and isothermal titration calorimetry.

    35. Zr-Substituted Polyoxometalate

      Modification of Tetranuclear Zirconium-Substituted Polyoxometalates – Syntheses, Structures, and Peroxidase-Like Catalytic Activities (pages 1926–1934)

      Dan Li, Huayan Han, Yonghui Wang, Xin Wang, Yangguang Li and Enbo Wang

      Article first published online: 20 NOV 2012 | DOI: 10.1002/ejic.201200791

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      New tetranuclear {Zr4}-containing polyoxometalates (POMs) modified by peroxido, mandelato, and acetato ligands were synthesized. The peroxido-modified {Zr4}-POMs exhibit peroxidase-like catalytic activity for the oxidation of the peroxidase substrate 3,3,5,5-tetramethylbenzidine (TMB) by H2O2.

    36. POM Catalysts

      Organoruthenium-Supported Polyoxotungstate – Synthesis, Structure and Oxidation of n-Hexadecane with Air (pages 1935–1942)

      Rui-Qi Meng, Bin Wang, Hui-Min Sui, Bao Li, Wei Song, Li-Xin Wu, Bing Zhao and Li-Hua Bi

      Article first published online: 16 JAN 2013 | DOI: 10.1002/ejic.201201037

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      A ruthenium complex and its polytungstate derivative have been synthesized and characterized. A solid catalyst of Ru-containing polytungstate anchored on SBA-15 modified with (3-aminopropyl)triethoxysilane was prepared, and its catalytic efficiency was assessed in the oxidation of n-hexadecane with air without any additives or solvents.

    37. Catalytic Epoxidation

      Investigation of the Reaction Mechanism for the Epoxidation of Alkenes with Hydrogen Peroxide Catalyzed by a Protonated Tetranuclear Peroxotungstate with NMR Spectroscopy, Kinetics, and DFT Calculations (pages 1943–1950)

      Ryo Ishimoto, Keigo Kamata and Noritaka Mizuno

      Article first published online: 4 DEC 2012 | DOI: 10.1002/ejic.201201058

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      A tetranuclear peroxotungstate [H{W2O2(O2)4(μ-O)}2]3– (I) showed high catalytic activity for epoxidation with H2O2. On the basis of the kinetic, mechanistic, spectroscopic, and theoretical investigations, it was found that I is the active species and that oxygen transfer from I to a C=C double bond is the rate-determining step.

    38. Solar Cells

      The Application of ZnO Nanoparticles Containing Polyoxometalates in Dye-Sensitized Solar Cells (pages 1951–1959)

      Jiansheng Li, Xiaojing Sang, Weilin Chen, Chao Qin, Shiming Wang, Zhongmin Su and Enbo Wang

      Article first published online: 12 FEB 2013 | DOI: 10.1002/ejic.201201120

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      The photoanode of a dye-sensitized solar cell is assembled with ZnO nanoparticles (NPs) containing polyoxometalates (POMs). The POMs in the ZnO NPs probably accept electrons from the conductor band of ZnO, which suppresses the backflow of electrons to the oxidized state of the dye and I3 ions in the redox electrolyte and improves the overall conversion efficiency.

    39. Phosphonium Decavanadates

      Tetraalkylphosphonium Decavanadates: Synthesis, Structures, and Solution Properties (pages 1960–1967)

      Sib Sankar Mal, Oliver Tröppner, Ivana Ivanović-Burmazović and Peter Burger

      Article first published online: 5 MAR 2013 | DOI: 10.1002/ejic.201201447

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      Four new phosphonium decavanadate hybrid materials have been synthesized and characterized by various spectroscopic methods. Single-crystal X-ray diffraction of IL01-V10 revealed that the [H3V10O28]6– anionic unit remains intact and that three phosphonium ionic liquid are electrostatically coupled to one decavanadate unit.

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