European Journal of Inorganic Chemistry

Cover image for Vol. 2016 Issue 21

Early View (Online Version of Record published before inclusion in an issue)

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.686

ISI Journal Citation Reports © Ranking: 2015: 12/46 (Chemistry Inorganic & Nuclear)

Online ISSN: 1099-0682

Associated Title(s): Angewandte Chemie International Edition, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemCatChem, Zeitschrift für anorganische und allgemeine Chemie

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  1. 1 - 83
  1. Full Papers

    1. Mixed Ln Clusters

      Nano-Nonanuclear Mixed-Lanthanide Clusters [Eu9–xTbx] Featuring Tunable Dual Luminescence Properties

      Djamila Guettas, Cristina M. Balogh, Camille Sonneville, Ylane Malicet, Florian Lepoivre, Emel Onal, Alexandra Fateeva, Christian Reber, Dominique Luneau, Olivier Maury and Guillaume Pilet

      Version of Record online: 28 JUL 2016 | DOI: 10.1002/ejic.201600412

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      New mixed [Eu9–xTbx] nanoclusters exhibit adjustable dual luminescence with strong TbIII to EuIII energy transfer through the fine control of the amounts of the lanthanide ions within the crystal structure.

  2. Communications

    1. Carbodiphosphoranes

      Difluoroborenium Cation Stabilized by Hexaphenyl-Carbodiphosphorane: A Concise Study on the Molecular and Electronic Structure of [(Ph3P)2C⇉BF2][BF4]

      Jörn E. Münzer, Pascual Oña-Burgos, Francisco M. Arrabal-Campos, Bernhard Neumüller, Ralf Tonner, Ignacio Fernández and Istemi Kuzu

      Version of Record online: 28 JUL 2016 | DOI: 10.1002/ejic.201600519

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      The reaction of C(PPh3)2 with BF3·OEt2 affords the difluoroborenium cation [CDP⇉BF2]+ (2+). Advanced NMR spectroscopy methods reveal strong ion pairing of 2+ with the [BF4] counterion in solution. Structural and computational studies show strong donor–acceptor interactions in which both the σ and π lone pairs of electrons of C(PPh3)2 donate into the vacant orbitals of [BF2]+.

  3. Full Papers

    1. Explosives

      Innovative Concept of Designing Primary Explosives by IntroducingPolymers: Preparation and Investigation of {[Ca(CHZ)2](ClO4)2}n (CHZ = carbohydrazide)

      Zhenhao Mi, Sitong Chen, Zhi Jing, Li Yang and Tonglai Zhang

      Version of Record online: 28 JUL 2016 | DOI: 10.1002/ejic.201600479

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      Coordination polymers were introduced to primary explosives. The remarkable structure of “discrete MOFs” makes great sense in the design of thermal-stable molecules with proper sensitivities.

    2. Platinum Coordination Modes

      Square-Planar PtII versus Octahedral PtIV Halido Complexes: 195Pt NMR Explained by a Simple Empirical Approach

      Michele Benedetti, Federica De Castro and Francesco P. Fanizzi

      Version of Record online: 27 JUL 2016 | DOI: 10.1002/ejic.201600573

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      The 195Pt NMR chemical shifts of octahedral [PtXnY6–n]2–, square-planar [PtXnY4–n]2–, and pentacoordinate [PtXY(η2-C2H4)(2,9-Me2-1,10-phen)] (X, Y = halido) vary linearly with the overall sum of the ionic radii of the halido ligands. The square-planar PtII complexes may be treated empirically as octahedral complexes in which the filled 5dz² orbital acts as two pseudo-halido ligands.

  4. Microreviews

    1. Postsynthetic Modification

      Postsynthetic Modification of Zirconium Metal-Organic Frameworks

      Ross J. Marshall and Ross S. Forgan

      Version of Record online: 27 JUL 2016 | DOI: 10.1002/ejic.201600394

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      The chemical and mechanical stabilities of zirconium metal-organic frameworks (MOFs) make them ideal platforms for postsynthetic modification. This microreview provides an overview of the various techniques for modification and the functionalities that can be incorporated into zirconium MOFs to facilitate different applications.

  5. Full Papers

    1. Magnetocaloric Effects

      Structure and Magnetocaloric Effect of Two Kinds of Ln–MnII Heterometallic Coordination Polymers Produced by Fractional Crystallization

      Gang Xiong, Li-xin You, Bao-yi Ren, Yong-ke He, Shu-ju Wang and Ya-guang Sun

      Version of Record online: 27 JUL 2016 | DOI: 10.1002/ejic.201600302

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      Two series of Ln–MnII heterometallic coordination polymers, Ln8Mn3 {Ln = Gd (1); Ln = Dy (2)}, Ln2Mn {Ln = Gd (3); Ln = Dy (4)} were synthesized by using fractional crystallization and structurally characterized. Polymers 14 exhibit large magnetic entropy changes of 42.0, 16.7, 31.5, and 16.6 J kg–1 K–1, respectively (ΔH = 7 T). In addition, compounds 2 and 4 displayed a slow magnetic relaxation.

    2. Mechanical Stability of MOFs

      The Impact of Mesopores on the Mechanical Stability of HKUST-1: A Multiscale Investigation

      Johannes P. Dürholt, Julian Keupp and and Rochus Schmid

      Version of Record online: 27 JUL 2016 | DOI: 10.1002/ejic.201600566

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      The impact of mesopores due to defects in HKUST-1 on surface areas and mechanical stability was investigated by a multiscale simulation approach, combining coarse-grained and atomistic methods. The mechanical stability is related to size and concentration of the mesopores, and unexpected trends in volumetric and gravimetric surface area are pointed out.

    3. Zr MOF Catalysts

      Diastereoselective Synthesis of Pyranoquinolines on Zirconium-Containing UiO-66 Metal-Organic Frameworks

      Víctor L. Rechac, Francisco G. Cirujano, Avelino Corma and Francesc X. Llabrés i Xamena

      Version of Record online: 25 JUL 2016 | DOI: 10.1002/ejic.201600372

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      Zirconium-containing UiO-66-type compounds catalyze the Povarov reaction between an imine and dihydropyran at room temperature to give trans-pyrano[3,2-c]quinoline with diastereomeric excesses of 90–95 %. The solids are stable and reusable catalysts that show no significant loss of activity or diastereoselectivity.

    4. Carbon Nitride Photocatalysis

      One-Pot Hydrothermal Synthesis of Visible-Light-Responsive MoS2/g-CNO Heterostructures for Organic-Pollutant Degradation

      Mega Joy, Balagopal N. Nair, Abdul Azeez Peer Mohamed, Krishna Gopakumar Warrier and Unnikrishnan Nair S. Hareesh

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/ejic.201600232

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      Heterojunction catalysts with MoS2 integrated into oxidized graphitic carbon nitride material are synthesized by a one-step hydrothermal route. The materials are reusable photocatalysts for the degradation of organic pollutants.

    5. Dynamic Coordination

      Kinetics and Thermodynamics of Constitutional Dynamic Coordination Systems Based on FeII, CoII, NiII, CuII, and ZnII

      Kitjanit Neranon and Olof Ramström

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/ejic.201600331

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      The constitutional dynamics of adaptive coordination systems based on FeII, CoII, NiII, CuII, and ZnII has been evaluated by ESI-MS and NMR. The resulting dynamic equilibration processes could be easily followed over time, and the kinetic and thermodynamic properties assessed.

    6. Gas Adsorption

      Observing the Effects of Shaping on Gas Adsorption in Metal-Organic Frameworks

      Nicolas Chanut, Andrew D. Wiersum, U-Hwang Lee, Young Kyu Hwang, Florence Ragon, Hubert Chevreau, Sandrine Bourrelly, Bogdan Kuchta, Jong-San Chang, Christian Serre and Philip L. Llewellyn

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/ejic.201600410

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      A series of four metal-organic frameworks were synthesized as powders and spheres, and these were characterized by gas adsorption at 30 °C coupled with microcalorimetry. Whereas most variations were expected, interesting effects including partial pore restriction and active site “protection” were also evidenced for some shaped materials, suggesting that the binder may play a more complex role.

    7. Luminescent Ru Complexes

      Luminescent Carbonyl Hydrido Ruthenium(II) Diimine Coordination Compounds: Structural, Photophysical, and Electrochemical Properties

      Fei Yu, Wing-Kin Chu, Chang Shen, Ya Luo, Jing Xiang, Shu-Qi Chen, Chi-Chiu Ko and Tai-Chu Lau

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/ejic.201600438

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      Luminescent carbonyl hydrido ruthenium(II) complexes with various diimine ligands have been synthesized. The effects of the electronic features and diimine ligand π-conjugation on the electronic and photophysical properties are discussed. The luminescence performance of these complexes could be significantly enhanced by increasing the rigidity and π-conjugation of the diimine ligand.

    8. Heterometallic Clusters

      Unprecedented 3D and 2D Frameworks of Manganese Thioarsenates Based on Heterometallic Cubic Cluster [Mn66-S)(AsS3)4] and Covalent Linker N2H4

      Chunying Tang, Yali Shen, Peipei Sun, ShuZhen Liu, Jingyu Han, Yun Liu, Hui Sun and Dingxian Jia

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/ejic.201600580

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      New Mn thioarsenates 1 and 2 based on the heterometallic cubic cluster [Mn6As4S13] were prepared with the assistance of the synergistic coordinating effect of hydrazine and ethylenepolyamine ligands. The 3D {[Mn66-S)(µ-N2H4)33-AsS3)4]2–} and 2D {[Mn66-S)(N2H4)2(µ-N2H4)23-AsS3)4]2–} clusters represent new types of structure and connectivity in compounds of the Mn/As/S family.

    9. Inorganic Pigments

      Unique Colours of 3d-Transition-Metal-Substituted Lyonsite Molybdates and Their Derivatives: The Role of Multiple Coordination Geometries and Metal-to-Metal Charge Transfer

      Sourav Laha, Srinivasan Natarajan and Jagannatha Gopalakrishnan

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/ejic.201600687

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      Lyonsite molybdates containing 3d transition metals display bright and unique colours that arise from both ligand-field electronic transitions in distorted octahedral coordination geometries and 3d-metal-to-4d-Mo charge transfer. Accordingly, the work identifies the lyonsite framework structure as a novel platform for developing new inorganic pigments.

    10. Substituted Phenanthrolines

      A Quantitative Description of the σ-Donor and π-Acceptor Properties of Substituted Phenanthrolines

      G. Attilio Ardizzoia, Michela Bea, Stefano Brenna and Bruno Therrien

      Version of Record online: 20 JUL 2016 | DOI: 10.1002/ejic.201600647

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      Like players of opponent teams in rugby, σ and π contributions are involved in a sort of “electronic scrum” that determines the nature of metal–ligand bonds. An ETS-NOCV study allowed us to quantify these contributions, associated with Eσ and Eπ, in [Mo(CO)4(phen*)] compounds. A new electronic parameter (Tphen) comprising both Eσ and Eπ has been introduced and correlated with experimental data.

    11. Mo Pentachloride in Catalysis

      One-Pot Intermolecular C–S Self-Coupling of Dimethyl Sulfoxide Promoted by Molybdenum Pentachloride

      Marco Bortoluzzi, Eleonora Ferretti, Mohammad Hayatifar, Fabio Marchetti, Guido Pampaloni and Stefano Zacchini

      Version of Record online: 20 JUL 2016 | DOI: 10.1002/ejic.201600611

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      The reactions between MoCl5 and limited amounts of a selection of sulfoxides are reported. The unusual, one-pot conversion of DMSO into a mercaptomethylsulfonium salt has been studied by means of X-ray crystallography, DFT calculations and spectroscopic and analytical techniques.

    12. Copper-Catalyzed Oxidation

      Dual Role of Acetate in Copper(II) Acetate Catalyzed Dehydrogenation of Chelating Aromatic Secondary Amines: A Kinetic Case Study of Copper-Catalyzed Oxidation Reactions

      Kesavapillai Sreenath, Zhao Yuan, Miguel Macias-Contreras, Vasanth Ramachandran, Ronald J. Clark and Lei Zhu

      Version of Record online: 19 JUL 2016 | DOI: 10.1002/ejic.201600540

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      The acetate ion accelerates the dehydrogenation of chelating secondary aromatic amines by acting as a base and a bridging ligand for the dinuclear copper catalytic center. The two-electron oxidation turnover-limiting step is therefore mediated by the redox conversion of a dicopper center from the +2 to +1 oxidation state.

    13. Cluster Compounds

      Five Disc-Shaped {MII7} (M = Mn, Fe, Co, Cu, Zn) and One Capsule-Like {CuII6NaI2} Clusters Assembled from an Identical Schiff Base Ligand

      Haifeng Zhang, Jin Zhang, Rui Liu, Yahong Li, Wei Liu and Wu Li

      Version of Record online: 19 JUL 2016 | DOI: 10.1002/ejic.201600455

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      Five transition-metal {MII7} clusters and one capsule-like {Cu6Na2} compound have been synthesized by employing an identical Schiff base ligand. Complex {CoII7} exhibits single molecule magnetic behavior.

    14. Intermetallic Phases

      Experimental and Theoretical Studies on the Crystal Structure of Ternary Copper Arsenides A2Cu3As3 (A = Sr, Eu)

      Rong Zhang, Ming-Yan Pan, Min Zhu, Xu-Tang Tao and Sheng-Qing Xia

      Version of Record online: 19 JUL 2016 | DOI: 10.1002/ejic.201600385

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      Two ternary copper-containing arsenides, Sr2Cu3As3 and Eu2Cu3As3, are synthesized, and their crystal structures are characterized by single-crystal XRD. The coexistence of ferromagnetic and antiferromagnetic order is observed. Theoretical calculations indicate that the Cu 3d orbitals make significant contributions around the Fermi level and also play an important role in the structure formation.

  6. Communications

    1. Sensors

      Multi-Readout Logic Gate for the Selective Detection of Metal Ions at the Parts Per Billion Level

      Nadia O. Laschuk, Iraklii I. Ebralidze, Denis Spasyuk and and Olena V. Zenkina

      Version of Record online: 18 JUL 2016 | DOI: 10.1002/ejic.201600606

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      A sensing platform for the rapid and sensitive detection of Fe2+, Fe3+, Ru3+, and Zn2+ in aqueous solutions is proposed. Boolean logic is applied to describe the interactions between the ligand (as a logic gate) and four target cations (logical inputs). The crystallographically determined structure of the [Fe(terpy-PO3Et2)2](ClO4)2 (terpy = 2,2′:6′,2′′-terpyridine) complex is presented.

  7. Full Papers

    1. Hetero-Trihalides

      Bonding Analysis in Homo- and Hetero-Trihalide Species: A Charge Displacement Study

      Gianluca Ciancaleoni, Massimiliano Arca, Giovanni F. Caramori, Gernot Frenking, Felipe S. S. Schneider and Vito Lippolis

      Version of Record online: 18 JUL 2016 | DOI: 10.1002/ejic.201600471

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      The bonding in homo- and hetero-trihalide species has been investigated by integrating charge displacement results in the function of the X1···X2 distance with energy decomposition analysis.

    2. Hollow Sandwiched Structures

      Formation of C@Fe3O4@C Hollow Sandwiched Structures with Enhanced Lithium-Storage Properties

      Xiaojian Ma, Lefei Huang, Fangfang Wu, Shenglin Xiong and Baojuan Xi

      Version of Record online: 18 JUL 2016 | DOI: 10.1002/ejic.201600432

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      C@Fe3O4@C hollow sandwiched composite structures are obtained by a hydrothermal process and are coated with a resorcinol–formaldehyde (RF) resin layer by the sol–gel method, followed by subsequent thermal treatment. The excellent electrochemical activities are due to the unique hollow sandwiched composite structure and good electrical conductivity.

    3. Polythreaded MOFs

      Formation of a Polythreaded, Metal–Organic Framework Utilizing an Interlocked Hexadentate, Carboxylate Linker

      Ghazale Gholami, Kelong Zhu, Jas S. Ward, Paul E. Kruger and Stephen J. Loeb

      Version of Record online: 18 JUL 2016 | DOI: 10.1002/ejic.201600311

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      A hexacarboxylate ligand based on an interlocked [2]rotaxane motif is used to construct a ZnII metal–organic framework material. The structure has a unique lattice, in which three independent 3-periodic frameworks are interpenetrated only by virtue of the threading of their individual components (axle and wheel) in the rotaxane linker.

    4. Dendritic Catalysts

      Synthesis, Characterization, and Catalytic Application of Mononuclear and Dendritic Cationic CuI Iminopyridine-Ligated Complexes in Aryl Iodide Hydroxylation

      Nomvano Mketo, Johan H. L. Jordaan, Anine Jordaan, Andrew J. Swarts and Selwyn F. Mapolie

      Version of Record online: 18 JUL 2016 | DOI: 10.1002/ejic.201600417

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      Mononuclear and dendritic cationic complexes bearing iminopyridine-based ligands have been evaluated as catalysts for the hydroxylation of 4-iodotoluene. A dendritic analogue displayed high catalytic activity and recyclability in neat water without requiring a phase-transfer agent. Catalyst deactivation in water was found to proceed by metal agglomeration.

    5. Organometallic Photochromic Systems

      Synthesis and Spectroscopic Studies of the Photochromism of Bifunctional Derivatives of Cymantrene in Solution and without Solvent

      Elena S. Kelbysheva, Lyudmila N. Telegina, Alexey N. Rodionov, Tatyana V. Strelkova, Mariam G. Ezernitskaya, Boris V. Lokshin and Nikolay M. Loim

      Version of Record online: 18 JUL 2016 | DOI: 10.1002/ejic.201600343

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      Solvent-free photoisomerization and thermal isomerization between olefin and amide chelates is accompanied by a distinctive color change and can be repeated at least three times without substantial changes to the spectral parameters of these photochromic systems.

    6. Lithiation

      Advanced NMR Methods and DFT Calculations on the Regioselective Deprotonation and Functionalization of 1,1′-Methylenebis(3-methylimidazole-2-thione)

      Mona Bauer, Dejan Premužić, Günther Thiele, Bernhard Neumüller, Ralf Tonner, Álvaro Raya-Barón, Ignacio Fernández and Istemi Kuzu

      Version of Record online: 18 JUL 2016 | DOI: 10.1002/ejic.201600323

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      The regioselective deprotonation and functionalization of 1,1′-methylenebis(3-methylimidazole-2-thione) is achieved through temperature control. The aggregation of the dilithiated species in the solid state and in solution is elucidated by X-ray analysis and NMR spectroscopy, respectively. Quantum chemical calculations of the deprotonation energies explain the reaction course.

    7. DNA Photoprobes

      Design and Photophysical Studies of Acridine-Based RuII Complexes for Applications as DNA Photoprobes

      Quentin Deraedt, Lionel Marcélis, Thomas Auvray, Garry S. Hanan, Frédérique Loiseau and Benjamin Elias

      Version of Record online: 14 JUL 2016 | DOI: 10.1002/ejic.201600468

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      RuII complexes bearing acridine-based ligands display relevant structures and photophysical behavior for their use as DNA photoprobes. Particularly, substitution of their terminal hydrogen by fluorine atoms allows tuning of the photophysical properties of the corresponding RuII complexes.

    8. Rhodium(III) Speciation

      Rhodium(III) Speciation in Concentrated Nitric Acid Solutions

      Danila Vasilchenko, Sofia Vorob'eva, Sergey Tkachev, Iraida Baidina, Anatoliy Belyaev, Sergey Korenev, Leonid Solovyov and Alexander Vasiliev

      Version of Record online: 14 JUL 2016 | DOI: 10.1002/ejic.201600523

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      Mononuclear complexes [Rh(H2O)6–n(NO3)n]3–n (n = 1–4) have been found to be the only form of RhIII existing in concentrated nitric acid solutions. For the first time, nitrato complexes of RhIII with four and six nitrato ligands have been isolated and structurally characterized.

    9. Ring-Opening Polymerization

      Magnesium and Zinc Complexes Supported by N,N,O Tridentate Ligands: Synthesis and Catalysis in the Ring-Opening Polymerization of rac-Lactide and α-Methyltrimethylene Carbonate

      Miao Huang and Haiyan Ma

      Version of Record online: 14 JUL 2016 | DOI: 10.1002/ejic.201600441

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      Magnesium and zinc complexes supported by biphenyl- or binaphthyl-based aminophenolate ligands efficiently initiated the ring-opening polymerization of rac-lactide (rac-LA) and α-methyltrimethylene carbonate (α-MeTMC), and gave relatively low heteroselectivities (Pr = 0.55–0.69) and high regioselectivities (Xreg = 0.81–0.93), respectively. Tol = toluene.

    10. Olefin Polymerization

      Yttrocene Chloride and Methyl Complexes with Variously Substituted Cyclopentadienyl Ligands: Synthesis, Characterization, and Reactivity toward Ethylene

      Adéla Fridrichová, Vojtech Varga, Jiří Pinkas, Martin Lamač, Aleš Růžička and Michal Horáček

      Version of Record online: 14 JUL 2016 | DOI: 10.1002/ejic.201600390

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      An ionic complex consisting of the tetranuclear anion {[(η5-C5Me4SiMe3)YCl2]44-Cl)} and the thf-coordinated lithium cation [Li(thf)4]+ was used for the synthesis of mixed yttrocene chloride and methyl complexes containing two cyclopentadienyl ligands with different steric demands. Yttrocene methyl complexes were tested as catalysts in ethylene polymerization.

  8. Communications

    1. Chirality at Metal Complexes

      Synthesis of Homochiral CoIII– and MnIV–[2.2]Paracyclophane Schiff Base Complexes with Predetermined Chirality at the Metal Centre

      Darran Loits, Stefan Bräse, Andrea J. North, Jonathan M. White, Paul S. Donnelly and Mark A. Rizzacasa

      Version of Record online: 14 JUL 2016 | DOI: 10.1002/ejic.201600750

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      A planar-chiral Schiff base [2.2]paracyclophane-derived ligand enabled the synthesis of homochiral cis-β-octahedral CoIII and MnIV metal complexes with complete control of the metal-centred chirality, and in the case of a di-µ-oxo MnIV complex, with (P)-helical chirality.

  9. Full Papers

    1. Confocal Microscopy Imaging

      Substitution of Metallocenes with [2.2]Paracyclophane to Enable Confocal Microscopy Imaging in Living Cells

      Joanna Skiba, Claudia Schmidt, Petra Lippmann, Philipp Ensslen, Hans-Achim Wagenknecht, Rafał Czerwieniec, Fabian Brandl, Ingo Ott, Tytus Bernaś, Barbara Krawczyk, Dominik Szczukocki and Konrad Kowalski

      Version of Record online: 13 JUL 2016 | DOI: 10.1002/ejic.201600281

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      The biodistribution of metallocenyl uracil–pyrenes is investigated through an indirect approach that exploits the structural similarities of metallocenyl and [2.2]paracyclophanyl groups. Confocal microscopy of a [2.2]paracyclophane uracil–pyrene shows its accumulation in the membranes, cytoplasm, and mitochondria. A similar biodistribution pattern is postulated for the metallocenyl congeners.

    2. Metallothionein Models

      Copper(I) Thiolate Heteroadamantane Cage Structures with Relevance to Metalloproteins

      Alexander Oppermann, Regina Dick, Christoph Wehrhahn, Ulrich Flörke, Sonja Herres-Pawlis and Gerald Henkel

      Version of Record online: 13 JUL 2016 | DOI: 10.1002/ejic.201600247

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      Herein, we present five new heteroadamantane copper(I) cluster complexes and a sixth decanuclear complex. Their structural relationship and comparability is highlighted by theoretical studies of the bonding and antibonding interactions within the molecular orbitals. These complexes show similarities to metallothioneins.

    3. Stannylenes

      Multiple Reactivity of SnII Complexes Bearing Catecholate and o-Amidophenolate Ligands

      Maxim G. Chegerev, Alexander V. Piskunov, Aryna V. Maleeva, Georgy K. Fukin and Gleb A. Abakumov

      Version of Record online: 13 JUL 2016 | DOI: 10.1002/ejic.201600501

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      Multiple modes of reactivity for selected stannylenes bearing redox-active catecholate and o-amidophenolate ligands towards different reagents are reported.

    4. Colloidal Nanocrystals

      Phase-Controlled Synthesis of Cu2SnS3 Nanocrystals: The Effect of Redox Conditions on the Initial Binary Cu2–xS Nucleation

      Qingshuang Liang

      Version of Record online: 12 JUL 2016 | DOI: 10.1002/ejic.201600447

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      Different phase components of zincblende and wurtzite mix-phase Cu2SnSe3 nanocrystals (NCs) were obtained. The phase selectivity of the Cu2SnSe3 NCs is related to the initial redox conditions. Wurtzite Cu2SnSe3 NCs formed because of the Cu31S16 seeds, and the CuS seeds led to zincblende structure Cu2SnSe3 NCs.

    5. Low-Coordinate P Chemistry

      Application of Imidazole-2-thione Substituents in Low-Coordinate Phosphorus Chemistry – Probing the Scope

      Paresh Kumar Majhi, Abhishek Koner, Gregor Schnakenburg, Zsolt Kelemen, László Nyulászi and Rainer Streubel

      Version of Record online: 12 JUL 2016 | DOI: 10.1002/ejic.201600703

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      2-Thioxoimidazole substituents have been investigated for the first time in the synthesis of low-coordinate phosphorus compounds of types IIII and revealed some surprising new features. The synthesis of some of the compounds have been studied computationally to provide further insights into some of the difficulties encountered in the syntheses.

  10. Communications

    1. Post-Synthetic Transformation

      Adding to the Arsenal of Zirconium-Based Metal–Organic Frameworks: the Topology as a Platform for Solvent-Assisted Metal Incorporation

      Tian-Fu Liu, Nicolaas A. Vermeulen, Ashlee J. Howarth, Peng Li, Amy A. Sarjeant, Joseph T. Hupp and Omar K. Farha

      Version of Record online: 8 JUL 2016 | DOI: 10.1002/ejic.201600627

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      NU-1200 is a Zr-based metal–organic framework (MOF) with the topology. Consisting of unsaturated Zr6 oxide nodes and triangular linkers with large interconnected channels, this MOF is an ideal candidate for postsynthesis metalation.

    2. Actinide Clusters

      First Evidence of a Water-Soluble Plutonium(IV) Hexanuclear Cluster

      Christelle Tamain, Thomas Dumas, Dominique Guillaumont, Christoph Hennig and Philippe Guilbaud

      Version of Record online: 8 JUL 2016 | DOI: 10.1002/ejic.201600656

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      The singular PuIV hexanuclear cluster [Pu6(OH)4O4]12+ is characterized in both the solid state and in water solution by using X-ray diffraction and X-ray absorption and UV/Vis spectroscopy. The stability of this cluster in water and its high solubility over a large pH range are of upmost importance for plutonium environmental speciation with potential applications in a related migration model.

  11. Full Papers

    1. Rare-Earth Chlorides

      Mono- and Dinuclear Rare-Earth Chlorides Ligated by a Mesityl-Substituted β-Diketiminate

      Svetlana V. Klementyeva, Mikhail Yu. Afonin, Artem S. Bogomyakov, Michael T. Gamer, Peter W. Roesky and Sergey N. Konchenko

      Version of Record online: 8 JUL 2016 | DOI: 10.1002/ejic.201600488

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      Dinuclear rare-earth metal complexes with an unusual triple chlorido bridge in the molecule [LClLn(µ-Cl)3LnL(THF)] and mononuclear complexes [LLnCl2(THF)2] were obtained by using a mesityl-substituted β-diketiminate as ligand L.

    2. Gold Clusters

      Polyhedral Bismuth Polycations Coordinating Gold(I) with Varied Hapticity in a Homoleptic Heavy-Metal Cluster

      Ulrike Müller, Anna Isaeva, Janine Richter, Maximilian Knies and Michael Ruck

      Version of Record online: 8 JUL 2016 | DOI: 10.1002/ejic.201600637

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      [Au(Bi8)2]5+ is a heavy-atom cluster in which polyhedral bismuth polycations coordinate a gold(I) atom in two different modes: η2 and η4. The cationic complex was obtained by ionothermal synthesis and is a rare example of bonding interactions between gold and bismuth.

    3. Palladium Catalysts

      Synthesis of Phosphanylferrocenecarboxamides Bearing Guanidinium Substituents and Their Application in the Palladium-Catalyzed Cross-Coupling of Boronic Acids with Acyl Chlorides

      Hana Charvátová, Ivana Císařová and Petr Štěpnička

      Version of Record online: 6 JUL 2016 | DOI: 10.1002/ejic.201600461

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      Phosphanylferrocene ligands 1 and 2 bearing guanidinium pendants have been prepared and utilized as donors in PdII complexes and in the Pd-catalyzed cross-coupling of arylboronic acids with benzoyl chlorides to give benzophenones. Consistently better results were achieved with ligand 2 possessing an extended alkylguanidinium moiety appended to the phosphanylferrocene unit through an amide moiety.

    4. Mechanical Properties of MOFs

      Impact of the Metal Centre and Functionalization on the Mechanical Behaviour of MIL-53 Metal–Organic Frameworks

      Pascal G. Yot, Ke Yang, Vincent Guillerm, Florence Ragon, Vladimir Dmitriev, Paraskevas Parisiades, Erik Elkaïm, Thomas Devic, Patricia Horcajada, Christian Serre, Norbert Stock, John P. S. Mowat, Paul A. Wright, Gérard Férey and Guillaume Maurin

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600263

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      The pressure-induced phase transitions of a series of hydrated MIL-53 metal–organic frameworks and their compressibility have been investigated as a function of the nature of both the metal centre and the functions grafted on to the organic linker.

    5. MOF Crystals as Precursors

      A Facile Synthesis of Co3O4 Hollow Microtubes by Decomposition of a Cobalt Metal–Organic Framework

      L. Claudia Gómez-Aguirre, Socorro Castro-García, Manuel Sánchez-Andújar, Susana Yáñez-Vilar, Jorge Mira, Juan Manuel Bermúdez-García, Teresa A. Centeno and María Antonia Señarís-Rodríguez

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600192

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      We obtained the metal–organic framework [Co2(NH2-bdc)2(dabco)]·[G] {G = H2O, N,N-dimethylformamide; NH2-bdc = 2-amino-1,4-benzenedicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane} as hollow microtubes and synthesized microtubular crystals of Co3O4 by calcination at 400 °C. The coordination-modulation method provides a simple route to nanostructured porous frameworks and derived oxides.

    6. Metals in Medicine

      Enhanced Antitumor Activity against Melanoma Cancer Cells by Nitric Oxide Release and Photosensitized Generation of Singlet Oxygen from Ruthenium Complexes

      Loyanne C. B. Ramos, Mario Sérgio Pereira Marchesi, Daniel Callejon, Marcelo Dias Baruffi, Claure N. Lunardi, Leonardo D. Slep, Lusiane M. Bendhack and Roberto Santana da Silva

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600217

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      The synergistic effect of nitric oxide and singlet oxygen originating from Ru complexes has been used to enhance the anticancer activity against B16/F10 cancer cells. The combination of reactive oxygen and nitrogen species (RONS) resulted in a decrease of cell viability up to 40 % compared with their presence in isolation. It seems that RONS activate intracellular molecules associated with cell death.

    7. Luminescent Mercury Complexes

      Topological Evolution in Mercury(II) Schiff Base Complexes Tuned through Alkyl Substitution – Synthesis, Solid-State Structures, and Aggregation-Induced Emission Properties

      Yu-Wei Dong, Rui-Qing Fan, Xin-Ming Wang, Ping Wang, Hui-Jie Zhang, Li-Guo Wei, Yang Song, Xi Du, Wei Chen and Yu-Lin Yang

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600231

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      Two series of mercury(II) complexes (Hg1a–Hg7a and Hg1b–Hg7b) are synthesized to investigate the influence of alkyl substituents on the construction of supramolecular metal–organic frameworks (SMOFs) and photoluminescence properties. Complexes Hg1a, Hg3a, Hg1b, and Hg3b exhibit good aggregation-induced emission (AIE) properties in CH3CN/H2O solutions.

    8. Bimetallic Complexes

      Synthesis and Structural Characterization of Mono- and Bimetallic Rhodium(I), Iridium(I) and Gold(I) Methanide and Methandiide Complexes from 2-Quinolyl-Linked (Thiophosphoranyl)methane

      Wing-Por Leung, Yuk-Chi Chan, Tsz-Hei Choi and Hung-Kay Lee

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600328

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      A series of mono- and bimetallic rhodium(I), iridium(I) and gold(I) metal complexes have been synthesized and structurally characterized by X-ray crystallography.

    9. MOF Morphology Control

      Controlling the Growth of Metal-Organic Frameworks Using Different Gravitational-Forces

      Joseph J. Richardson, Kang Liang, Fabio Lisi, Mattias Björnmalm, Matthew Faria, Junling Guo and Paolo Falcaro

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600338

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      Metal-organic frameworks (MOFs) are grown under different gravitational forces. We demonstrate that larger MOFs grow at lower g-force (g < 1), while smaller MOFs grow at higher g-force (g = 20). This data matches well with historical studies on crystal growth in microgravity, suggesting that the MOFs explored herein are governed by similar growth mechanisms to a wide variety of other crystals.

    10. Phosphorus Heterocycles

      1,1- and 1,4-Addition Reactions with 3a,6a-Diaza-1,4-diphosphapentalene Containing Two-Coordinate and Formally Divalent Phosphorus

      Alexander N. Kornev, Vadim E. Galperin, Vyacheslav V. Sushev, Natalia V. Zolotareva, Evgenii V. Baranov, Georgy K. Fukin and Gleb A. Abakumov

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600348

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      DDP reacts with benzyl chloride and chlorotriphenylmethane leading to 1,1- and 1,4-addition products, respectively. The 1,1-adduct of benzyl chloride contains hypervalent phosphorus showing a N···P nonvalent interaction.

    11. Tellurates

      The High-Pressure Polymorph of Ca4Te5O14 and the Mixed-Valent Compound Ca13TeVI2/3TeIV3.75O15(BO3)4(OH)3

      Matthias Weil, Gunter Heymann and Hubert Huppertz

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600429

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      Two new structure types have been elucidated during the high-pressure synthesis of calcium oxotellurates. The high-pressure polymorph of Ca4Te5O14 is compared with its ambient counterpart and Ca13TeVI2/3TeIV3.75O15(BO3)4(OH)3 is the first phase reported to contain both oxoborate and oxotellurate units. Face-sharing of TeVI and TeIV oxopolyhedra in the crystal structure of the latter is unprecedented in the crystal chemistry of oxotellurates.

    12. Fluorescent Probes

      Acid–Base Behaviour in the Absorption and Emission Spectra of Ruthenium(II) Complexes with Hydroxy-Substituted Bipyridine and Phenanthroline Ligands

      Fei Yu, Chang Shen, Tao Zheng, Wing-Kin Chu, Jing Xiang, Ya Luo, Chi-Chiu Ko, Zheng-Qing Guo and Tai-Chu Lau

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600460

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      A series of [RuII(bpy)2(N-N)](BF4)2 complexes bearing hydroxy-substituted diimine ligands have been synthesized and characterized. Photophysical studies showed that the luminescent properties of these complexes are sensitive to the nature of the solvent media. They also exhibit strong dependence on the pH of the aqueous medium, and hence these complexes have potential as phosphorescent pH probes.

    13. Carbene Phosphinidenes

      Transition-Metal Carbonyl Complexes and Electron-Donating Properties of N-Heterocyclic-Carbene–Phosphinidene Adducts

      Dirk Bockfeld, Adinarayana Doddi, Peter G. Jones and Matthias Tamm

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600483

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      A series of metal carbonyl complexes supported by N-heterocyclic-carbene–phosphinidene adducts are synthesized. The very low carbonyl stretching frequencies of these complexes in comparison with those of selected phosphines and N-heterocyclic carbenes indicate the strong electron-donating character of these newly emerging low-valent phosphorus ligands.

    14. Sb and Bi Chalcogenides

      Alternative Precursors for the Synthesis of Binary Sb2E3 and Bi2E3 (E = S, Se, Te) Nanoparticles by the Hot Injection Method

      Monika Rusek, Georg Bendt, Christoph Wölper and Stephan Schulz

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600490

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      Binary antimony (Sb2E3) and bismuth chalcogenide (Bi2E3) nanoparticles were obtained by reaction of Sb(OCH2CH2NMe2)3 and Bi(OCH2CH2NMe2)3 with (R3Si)2E (E = S, Se, Te; R = Me, Et) at moderate temperatures. The reactions were studied by in situ 1H NMR spectroscopy, and the products were characterized by energy-dispersive X-ray spectroscopy, XRD, IR spectroscopy, and SEM.

    15. Conducting MOFs

      Conducting Behavior and Valence Ordering of a One-Dimensional MMX-Type Coordination Polymer under High Pressure

      Kazuya Otsubo, Tomohiko Suto, Atsushi Kobayashi, Ryuichi Ikeda, Masato Hedo, Yoshiya Uwatoko and Hiroshi Kitagawa

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600499

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      We report on the conducting behavior and electronic state of a highly conductive MMX-type coordination polymer, Pt2(dta)4I (dta: CH3CS2), under high pressure. This compound shows semiconducting behavior up to 8 GPa. Raman and X-ray diffraction (XRD) studies clearly revealed the electronic states under pressure. In addition, the pressure–temperature phase diagram of this compound was clarified.

    16. Single-Ion Magnets

      Field-Induced Single-Ion-Magnetic Behavior of Octahedral CoII in a Two-Dimensional Coordination Polymer

      Amit Kumar Mondal, Sajal Khatua, Kapil Tomar and Sanjit Konar

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600569

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      Two-dimensional coordination polymers have been synthesized by using 4′-(4-methoxyphenyl)-4,2′:6′,4′′-terpyridine as ligand and CoII or FeII salts. The CoII-based coordination polymer exhibits field-induced single-ion-magnet behavior.

    17. Core–Shell Particles

      ZnO@ZIF Core–Shell Single Crystals Formed by in Situ Conversion of ZnO Particles

      Ying Sun, Qing Zhang, Xiaona Xu, Lin Zhang, Zhengming Wu, Jun Guo and Guang Lu

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600590

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      ZnO@ZIF-8 and ZnO@ZIF-71 core–shell single crystals can be synthesized by the in situ conversion of ZnO particles under optimized experimental conditions. The formation of these hybrid ZIF single crystals is attributed to the single-site heterogeneous nucleation and growth of ZIF on the ZnO surfaces but depends strongly on the reaction solvent, ligand concentration and ZnO particle size.

    18. Distorted Porphyrins

      Formation of π-Cation Radicals in Highly Deformed Copper(II) Porphyrins: Implications for the Distortion of Natural Tetrapyrrole Macrocycles

      Zaichun Zhou, Min Tang, Qiuhua Liu, Xi Zhang and Xiaochun Zhou

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600674

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      The electronic structure of the CuII ion can be tuned through the activation of its unpaired electron under the strong compression of core in a highly ruffled porphyrin, and the activated electron can be stabilized as a π-cation radical in the cage complex. This study indicates that the activation of an electron in a CuII ion only requires the contraction of the core.

    19. Borate-Nitrates

      Syntheses, Structure Elucidation, and Characterization of the Borate-Nitrates RE[B5O8(OH)(H2O)x]NO3·2H2O [RE = Nd (x = 0.85), Sm (x = 0)]

      Teresa S. Ortner, Klaus Wurst, Bastian Joachim and Hubert Huppertz

      Version of Record online: 28 JUN 2016 | DOI: 10.1002/ejic.201600480

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      New borate-nitrates containing Nd3+ and Sm3+ have been synthesized hydrothermally from rare-earth nitrate hydrates and an excess of boric acid. X-ray, Raman, and IR characterizations of the new structural variants of Ce[B5O8(OH)(H2O)]NO3·2H2O are presented.

    20. MOF Composites in Theranostics

      A Promising Catalytic and Theranostic Agent Obtained through the In-Situ Synthesis of Au Nanoparticles with a Reduced Polyoxometalate Incorporated within Mesoporous MIL-101

      Catherine Roch-Marchal, Tania Hidalgo, Hung Banh, Roland A. Fischer and Patricia Horcajada

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/ejic.201600359

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      Promising catalysts and optical contrast agents based on (Au)POM@MOF (POM = polyoxometalate, MOF = metal–organic framework) composites are synthesized in situ through the incorporation of a POM into the mesopores of MIL-101, followed by reduction to form Au nanoparticles. These composites are internalized rapidly by cells, and no Au/POM leaching or MOF biodegradation occurs.

    21. Fluorinated Phosphoranes

      Difluorotriorganylphosphoranes for the Synthesis of Fluorophosphonium and Bismuthonium Salts

      Sven Solyntjes, Beate Neumann, Hans-Georg Stammler, Nikolai Ignat'ev and Berthold Hoge

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/ejic.201600539

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      Highly reactive fluorophosphonium cations, [R3PF]+, previously unknown fluorobismuthonium cations, [R3BiF]+, and triarylbismuth dications, [R3Bi]2+, are conveniently available by the reactions of difluoro(triaryl)pnictogens with new difluoro(perfluoroorganyl)phosphoranes.

  12. Microreviews

    1. Hydrogen Isotope Separation

      You have full text access to this OnlineOpen article
      Quantum Sieving for Separation of Hydrogen Isotopes Using MOFs

      Hyunchul Oh and Michael Hirscher

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600253

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      Two mechanisms for hydrogen isotope separation using MOFs are introduced: “kinetic quantum sieving (KQS) with confinement in small pores” and “chemical affinity quantum sieving (CAQS) by strong adsorption sites”. In addition, the recent status and future strategies for hydrogen isotope separation with the aid of MOFs is discussed.

  13. Full Papers

    1. MOFs for Sensors

      Vapochromic Luminescence of a Zirconium-Based Metal–Organic Framework for Sensing Applications

      Franziska Drache, Volodymyr Bon, Irena Senkovska, Marcus Adam, Alexander Eychmüller and Stefan Kaskel

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600261

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      Integration of fluorenone cores into a zirconium metal–organic framework (MOF) results in sensitive vapochromic luminescence. The MOF shows significant changes in the emission spectrum in response to solvent-vapour exposure, which makes this material a potential candidate for luminescence-based sensing applications.

    2. Phosphorus Biradicaloids

      Synthesis of a Silylated Phosphorus Biradicaloid and Its Utilization in the Activation of Small Molecules

      Alexander Hinz, René Kuzora, Anne-Kristin Rölke, Axel Schulz, Alexander Villinger and Ronald Wustrack

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600321

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      Silylated 1,3-dichloro-1,3-diphospha-2,4-diazane, [ClP(µ-NHyp)]2 [Hyp = Si(SiMe3)3], was reduced with activated magnesium to afford the silylated biradicaloid [P(µ-NHyp)]2, which was isolation and fully characterized. The activation of molecules bearing single and double bonds with [P(µ-NHyp)]2 was studied, yielding heteroatom cage compounds.

    3. Single-Molecule Magnets

      Tri- and Pentanuclear Complexes Derived from Manganese(III) Schiff Base and Hexacyanoferrate(III) Building Blocks

      Meng-Jiao Zhang, Yu-Ye Zhang, Chun Yang, Qing-Lun Wang and Dai-Zheng Liao

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600339

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      Two cyanido-bridged complexes are synthesized from the same [Mn(SB)(H2O)]+ (SB = Schiff base) and hexacyanoferrate(III) reactants. The first complex consists of cyanido-bridged linear trinuclear [{Mn(SB)}2{Fe(CN)6}] anions, which are further linked into 1D chains by biphenolate bridges. The second complex is a cyanido-bridged pentanuclear complex, which behaves as a single-molecule magnet.

    4. Anion Radical Complexes

      Mixed-Valence o-Iminobenzoquinone and o-Iminobenzosemiquinonate Anion Radical Complexes of Cobalt: Valence Tautomerism

      Suvendu Maity, Suman Kundu, Sachinath Bera, Thomas Weyhermüller and Prasanta Ghosh

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600525

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      o-Iminobenzosemiquinonate anion radical (LSPhISQ·) and o-iminobenzoquinone (LSPhIQ) based mixed-valence complexes of cobalt of the types trans-[CoII(LSPhISQ0.5·)2X] {X = Cl, SCN(thiocyanato-kS), N3, NO2, and I3} (LSPhH2 = 2,4-di-tert-butyl-6-{[2-(phenylthio)phenyl]amino}phenol), which exhibit valence tautomerism in both solid and solution states are reported.

    5. o-Iminobenzoquinone and o-Iminobenzosemiquinonate Anion Radical Complexes of Rhodium and Ruthenium

      Suvendu Maity, Suman Kundu, Sachinath Bera, Thomas Weyhermüller and Prasanta Ghosh

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600526

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      o-Iminobenzosemiquinonate anion radical (LSPhISQ·) and o-iminobenzoquinone (LSPhIQ) complexes of rhodium and ruthenium of types cis-[RhIII(LSPhISQ·)(PPh3)Cl2] (1) and cis-[RuII(LSPhIQ)(PPh3)Cl2] (2) (LSPhH2 = 2,4-di-tert-butyl-6-{[2-(phenylthio)phenyl]amino}phenol) are reported. The existence of valence tautomeric equilibrium of type [RhIII(LSPhISQ·)] ⇌ [RhII(LSPhIQ)] in 1 was established.

    6. Gas Separation

      Flexible Metal–Organic Frameworks with Discriminatory Gate-Opening Effect for the Separation of Acetylene from Ethylene/Acetylene Mixtures

      Libo Li, Rajamani Krishna, Yong Wang, Xiaoqing Wang, Jiangfeng Yang and Jinping Li

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600182

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      Two flexible metal–organic frameworks (MOFs) exhibit gate-opening-type adsorption properties for acetylene but not for ethylene, leading to a highly selective adsorption of acetylene over ethylene at 273–298 K. The results suggest the potential of both flexible MOFs for industrial acetylene/ethylene separation through the energy-efficient adsorption separation process.

  14. Communications

    1. Proton-Conducting MOFs

      10000-Fold Enhancement in Proton Conduction by Doping of Cesium Ions in a Proton-Conducting Zwitterionic Metal–Organic Framework

      Sorout Shalini, Shubhangi Aggarwal, Santosh K. Singh, Malvika Dutt, Thallaseril G. Ajithkumar and Ramanathan Vaidhyanathan

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/ejic.201600364

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      Partial replacement of protons from a zwitterionic pyridinol of a Mg(terephthalate) metal–organic framework by about 10 % Cs+ ions provides a 10000-fold enhancement in proton conductivity. The concentration of Cs+ needs to be optimal to realize this maximum enhancement.

  15. Full Papers

    1. Continuous Synthesis

      A Facile “Green” Route for Scalable Batch Production and Continuous Synthesis of Zirconium MOFs

      Helge Reinsch, Steve Waitschat, Sachin M. Chavan, Karl Petter Lillerud and Norbert Stock

      Version of Record online: 16 JUN 2016 | DOI: 10.1002/ejic.201600295

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      A “green” preparative route for the synthesis of zirconium MOFs with diverse topologies was developed. This allows the synthesis of multigram amounts in batch reactions or under continuous flow conditions.

    2. Carbon Dioxide Capture

      Quantitative Structure–Property Relationship Models for Recognizing Metal Organic Frameworks (MOFs) with High CO2 Working Capacity and CO2/CH4 Selectivity for Methane Purification

      Mohammad Zein Aghaji, Michael Fernandez, Peter G. Boyd, Thomas D. Daff and Tom K. Woo

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/ejic.201600365

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      Robust machine learning QSPR models have been developed to accurately recognize high-performing metal organic framework materials for both the working capacity and selectivity in CO2/CH4 gas separations under methane purification conditions. The models were trained on 32,500 MOFs and validated on a test set of ca. 290,000 hypothetical MOFs.

  16. Communications

    1. Mixed–Matrix Membranes

      Increased Selectivity in CO2/CH4 Separation with Mixed-Matrix Membranes of Polysulfone and Mixed-MOFs MIL-101(Cr) and ZIF-8

      Harold B. Tanh Jeazet, Sara Sorribas, José M. Román-Marín, Beatriz Zornoza, Carlos Téllez, Joaquín Coronas and Christoph Janiak

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/ejic.201600190

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      Combination of two different MOFs [MIL-101(Cr) and ZIF-8] in the same MMM produces synergy effects with significant increase of CO2/CH4 selectivity compared to analogous MMMs with only one filler type.

    2. Tuning of MOF Synthesis

      Modulated Synthesis of Metal-Organic Frameworks through Tuning of the Initial Oxidation State of the Metal

      Mathieu Bosch, Xing Sun, Shuai Yuan, Ying-Pin Chen, Qi Wang, Xuan Wang and Hong-Cai Zhou

      Version of Record online: 10 JUN 2016 | DOI: 10.1002/ejic.201600211

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      In this work, we introduce a new method for the tuning of MOF synthesis: modulation through alteration of the metal source's initial oxidation state. This concept is demonstrated through the synthesis of PCN-47, PCN-48, and PCN-49, MOFs with distinct structures and porosities synthesized from the same metal and ligand with the metal initially in different oxidation states.

  17. Full Papers

    1. Proton-Conducting MOFs

      Proton Conductivities Manipulated by the Counter-Anions in 2D Co-Ca Coordination Frameworks

      Song-Song Bao, Yu-Xuan Wu, Nan-Zhu Li and Li-Min Zheng

      Version of Record online: 10 JUN 2016 | DOI: 10.1002/ejic.201600203

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      This work provides a new route to enhance proton conductivities of metal-organic framework materials by tuning the size, shapes and hydrogen-bonding capabilities of the counter-anions.

  18. Communications

    1. Thermochromism

      Anomalous Thermal Expansion and Luminescence Thermochromism in Silver(I) Dicyanamide

      Sarah A. Hodgson, Sarah J. Hunt, Thomas Just Sørensen, Amber L. Thompson, Emily M. Reynolds, Stephen Faulkner and Andrew L. Goodwin

      Version of Record online: 10 JUN 2016 | DOI: 10.1002/ejic.201600246

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      Silver(I) dicyanamide exhibits both mechanical and optical sensitivity to temperature. This responsive metal–organic framework may find application in high-precision temperature sensors.

  19. Microreviews

    1. “Green” Synthesis

      “Green” Synthesis of Metal-Organic Frameworks

      Helge Reinsch

      Version of Record online: 9 JUN 2016 | DOI: 10.1002/ejic.201600286

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      During the recent years the research in the field of MOFs has gradually shifted towards a focus on more sustainable and industrially feasible conditions. This microreview gives several concise examples from this emerging field of research and also depicts some perspectives.

  20. Full Papers

    1. MOF Polymer Membranes

      Luminescent Metal–Organic Framework Mixed-Matrix Membranes from Lanthanide Metal–Organic Frameworks in Polysulfone and Matrimid

      Janina Dechnik, Friedrich Mühlbach, Dennis Dietrich, Tobias Wehner, Marcus Gutmann, Tessa Lühmann, Lorenz Meinel, Christoph Janiak and Klaus Müller-Buschbaum

      Version of Record online: 30 MAY 2016 | DOI: 10.1002/ejic.201600235

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      The luminescent metal–organic framework/polymer (MOF–polymer) mixed-matrix membranes 3[Sr0.9Eu0.1Im2]@PSF (Im = imidazolate, PSF = polysulfone), 3[Sr0.9Eu0.1Im2]@Matrimid, and 2[Tb2Cl6(bipy)3]·2bipy@PSF (bipy = 4,4-bipyridine) are prepared with the polysulfone Ultrasonî S and Matrimidî. Thereby, MOF luminescence can be maintained and transferred into processable polymer membranes.

    2. MOFs and Sensors

      A Three-Dimensional Tetraphenylíethene-Based Metal–Organic Framework for Selective Gas Separation and Luminescence Sensing of Metal Ions

      Wei Yang, Ganggang Chang, Hailong Wang, Tong-Liang Hu, Zizhu Yao, Khalid Alfooty, Shengchang Xiang and Banglin Chen

      Version of Record online: 18 MAY 2016 | DOI: 10.1002/ejic.201600201

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      A three-dimensional multifunctional metal–organic framework (MOF), UTSA-86, made up of cadmium ions and a tetraphenylethene-based tetracarboxylate ligand has been synthesized and characterized by single-crystal X-ray diffraction analysis. This MOF exhibits permanent porosity, selective gas uptake, and luminescence sensing of metal ions.

  21. Microreviews

    1. Phosphonate MOFs

      Robust Metal-Organic Frameworks Based on Tritopic Phosphonoaromatic Ligands

      Marco Taddei, Ferdinando Costantino and Riccardo Vivani

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/ejic.201600207

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      Tritopic phosphonoaromatic ligands have recently been used with the aim of synthesizing microporous compounds. The most relevant results are reviewed.

  22. Communications

    1. Carbon Dioxide Fixation

      Anionic Metal–Organic Framework for Selective Dye Removal and CO2 Fixation

      Sanjay Kumar, Gaurav Verma, Wen-Yang Gao, Zheng Niu, Lukasz Wojtas and Shengqian Ma

      Version of Record online: 27 APR 2016 | DOI: 10.1002/ejic.201600218

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      A microporous Zn-based anionic metal–organic framework (MOF) is synthesized with triangular 4,4′,4″-(pyridine-2,4,6-triyl)tribenzoic acid; it features open channels and proves to be a good capturing agent for cationic dyes. In addition, the Zn-MOF demonstrates excellent catalytic activity for CO2 fixation by cycloaddition reaction with epoxides.

  23. Full Papers

    1. Porous MOFs

      Carboxylate–Hydrazone Mixed-Linker Metal–Organic Frameworks: Synthesis, Structure, and Selective Gas Adsorption

      Kornel Roztocki, Irena Senkovska, Stefan Kaskel and Dariusz Matoga

      Version of Record online: 21 APR 2016 | DOI: 10.1002/ejic.201600134

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      Two metal–organic frameworks incorporating carboxylate and acylhydrazone moieties are constructed from 4-pyridinecarbaldehyde isonicotinoyl hydrazone (PCIH) and linear dicarboxylate [dcx = 1,4-benzene- (BDC) or 4,4′-biphenyldicarboxylate (BPDC)]. Interpenetrated pillar-layered [Zn2(dcx)2(PCIH)2] frameworks selectively adsorb CO2 over N2.

    2. Arsenic Remediation

      Fe3O4@MIL-101 – A Selective and Regenerable Adsorbent for the Removal of As Species from Water

      Karel Folens, Karen Leus, Nina Ricci Nicomel, Maria Meledina, Stuart Turner, Gustaaf Van Tendeloo, Gijs Du Laing and Pascal Van Der Voort

      Version of Record online: 21 APR 2016 | DOI: 10.1002/ejic.201600160

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      MIL-101(Cr) serves as a host for the in situ synthesis of Fe3O4 nanoparticles. The resulting material shows excellent affinity towards AsIII and AsV species in water. Ca2+, Mg2+, and phosphate ions as well as natural organic matter do not affect the removal efficiency or selectivity. The structural integrity of the host is maintained during the adsorption and desorption process.

  24. Communications

    1. Supported Nanocatalysts

      High Catalytic Performance of MIL-101-Immobilized NiRu Alloy Nanoparticles towards the Hydrolytic Dehydrogenation of Ammonia Borane

      Sandipan Roy, Pradip Pachfule and Qiang Xu

      Version of Record online: 19 APR 2016 | DOI: 10.1002/ejic.201600180

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      Ultrafine NiRu alloy nanoparticles are successfully immobilized in the pores of MIL-101 by the double-solvent method combined with the overwhelming reduction approach. The immobilized nanoparticles show high catalytic performance towards the hydrolytic dehydrogenation of ammonia borane.

    2. Carbon Dioxide Reduction

      A Rhenium-Functionalized Metal–Organic Framework as a Single-Site Catalyst for Photochemical Reduction of Carbon Dioxide

      Ruiyun Huang, Yu Peng, Cheng Wang, Zhan Shi and Wenbin Lin

      Version of Record online: 5 APR 2016 | DOI: 10.1002/ejic.201600064

      Thumbnail image of graphical abstract

      A (bpy)Re(CO)3Cl-containing metal–organic framework (MOF) acts as an effective single-site catalyst to photochemically reduce carbon dioxide to carbon monoxide and formate. Mechanistic insights into the monomolecular pathway of the photocatalytic CO2 reduction have been obtained without interference from bimolecular pathways, thanks to site-isolation of the catalytic centers in MOFs.

    3. Post-Synthetic Transformation

      SALE-Ing a MOF-Based “Ship of Theseus.” Sequential Building-Block Replacement for Complete Reformulation of a Pillared-Paddlewheel Metal-Organic Framework

      Yan Xu, Nicolaas A. Vermeulen, Yangyang Liu, Joseph T. Hupp and Omar K. Farha

      Version of Record online: 18 MAR 2016 | DOI: 10.1002/ejic.201600069

      Thumbnail image of graphical abstract

      Text for Table of Contents: Interchange of a non-interpenetrating Zn based pillared-paddlewheel MOF into an entirely different Ni-based pillared-paddlewheel MOF has been achieved through the combination of solvent assisted linker exchange and transmetalation.

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