Harald Krautscheid

Publications (40)169.49 Total impact

• Article: Synthesis, Crystal Structure, and Solid-State NMR Investigations of Heteronuclear Zn/Co Coordination Networks - A Comparative Study.

  Anusree Viswanath Kuttatheyil, Daniel Lässig, Jörg Lincke, Merten Kobalz, Maria Baias, Katja König, Jörg Hofmann, Harald Krautscheid, Chris J Pickard, Jürgen Haase, Marko Bertmer
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  ABSTRACT: Synthesis and solid-state NMR characterization of two isomorphous series of zinc and cobalt coordination networks with 1,2,4-triazolyl benzoate ligands are reported. Both series consist of 3D diamondoid networks with four-fold interpenetration. Solid-state NMR identifies the metal coordination of the ligands, and assignment of all (1)H and (13)C shifts was enabled by the combination of (13)C editing, FSLG-HETCOR spectra, and 2D (1)H-(1)H back-to-back (BABA) spectra with results from NMR-CASTEP calculations. The incorporation of Co(2+) replacing Zn(2+) ions in the MOF over the full range of concentrations has significant influences on the NMR spectra. A uniform distribution of metal ions is documented based on the analysis of (1)H T1 relaxation time measurements.
  Inorganic Chemistry 04/2013; · 4.60 Impact Factor
• Article: Synthesis, Crystal Structure, and Solid-State NMR Investigations of Heteronuclear Zn/Co Coordination Networks - A Comparative Study

  Anusree Viswanath Kuttatheyil, Daniel Lässig, Jörg Lincke, Merten Kobalz, Maria Baias, Katja König, Jörg Hofmann, Harald Krautscheid, Chris J. Pickard, Jürgen Haase, and Marko Bertmer
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  ABSTRACT: Anusree Viswanath Kuttatheyil,† Daniel Lässig,‡ Jörg Lincke, Merten Kobalz,Maria Baias, Katja König, Jörg Hofmann, Harald Krautscheid, Chris J. Pickard,Jürgen Haase,and Marko Bertmer
  Inorganic Chemistry 03/2013; · 4.60 Impact Factor
• Article: Functionalized Adamantane Tectons Used in the Design of Mixed-Ligand Copper(II) 1,2,4-Triazolyl/Carboxylate Metal-Organic Frameworks.

  Ganna A Senchyk, Andrey B Lysenko, Harald Krautscheid, Eduard B Rusanov, Alexander N Chernega, Karl W Krämer, Shi-Xia Liu, Silvio Decurtins, Konstantin V Domasevitch
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  ABSTRACT: Bistriazoles, 1,3-bis(1,2,4-triazol-4-yl)propane (tr(2)pr) and 1,3-bis(1,2,4-triazol-4-yl)adamantane (tr(2)ad), were examined in combination with the rigid tetratopic 1,3,5,7-adamantanetetracarboxylic acid (H(4)-adtc) platform for the construction of neutral heteroleptic copper(II) metal-organic frameworks. Two coordination polymers, [{Cu(4)(OH)(2)(H(2)O)(2)}{Cu(4)(OH)(2)}(tr(2)pr)(2)(H-adtc)(4)]·2H(2)O (1) and [Cu(4)(OH)(2)(tr(2)ad)(2)(H-adtc)(2)(H(2)O)(2)]·3H(2)O (2), were synthesized and structurally characterized. In complexes 1 and 2, the N(1),N(2)-1,2,4-triazolyl (tr) and μ(3)-OH(-) groups serve as complementary bridges between adjacent metal centers supporting the tetranuclear dihydroxo clusters. The structure of 1 represents a unique association of two different kinds of centrosymmetrical {Cu(4)(OH)(2)} units in a tight 3D framework, while in compound 2, another configuration type of acentric tetranuclear metal clusters is organized in a layered 3,6-hexagonal motif. In both cases, the {Cu(4)(OH)(2)} secondary building block and trideprotonated carboxylate H-adtc(3-) can be viewed as covalently bound six- and three-connected nodes that define the net topology. The tr ligands, showing μ(3)- or μ(4)-binding patterns, introduce additional integrating links between the neighboring {Cu(4)(OH)(2)} fragments. A variable-temperature magnetic susceptibility study of 2 demonstrates strong antiferromagnetic intracluster coupling (J(1) = -109 cm(-1) and J(2) = -21 cm(-1)), which combines for the bulk phase with a weak antiferromagnetic intercluster interaction (zj = -2.5 cm(-1)).
  Inorganic Chemistry 01/2013; · 4.60 Impact Factor
• Article: Ag(I)/V(V) heterobimetallic frameworks generated from novel-type {Ag2(VO2F2)2(triazole)4} secondary building blocks: a new aspect in the design of SVOF hybrids.

  Ganna A Senchyk, Valeriy O Bukhan'ko, Andrey B Lysenko, Harald Krautscheid, Eduard B Rusanov, Alexandr N Chernega, Miroslaw Karbowiak, Konstantin V Domasevitch
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  ABSTRACT: A series of new silver(I)-containing MOFs [Ag(2)(tr(2)ad)(2)](ClO(4))(2) (1), [Ag(2)(VO(2)F(2))(2)(tr(2)ad)(2)]·H(2)O (2), [Ag(2)(VO(2)F(2))(2)(tr(2)eth)(2)(H(2)O)(2)] (3), and [Ag(2)(VO(2)F(2))(2)(tr(2)cy)(2)]·4H(2)O (4) supported by 4-substituted bifunctional 1,2,4-triazole ligands (tr(2)ad = 1,3-bis(1,2,4-triazol-4-yl)adamantane, tr(2)eth = 1,2-bis(1,2,4-triazol-4-yl)ethane, tr(2)cy = trans-1,4-bis(1,2,4-triazol-4-yl)cyclohexane) were hydrothermally synthesized and structurally characterized. In these complexes, the triazole heterocycle as an N(1),N(2)-bridge links either two adjacent Ag-Ag or Ag-V centers at short distances forming polynuclear clusters. The crystal structure of compound 1 is based on cationic {Ag(2)(tr)(4)}(2+) fragments connected in a 2D rhombohedral grid network with (4,4) topology. The neighboring layers are tightly packed into a 3D array by means of argentophilic interactions (Ag···Ag 3.28 Å). Bridging between different metal atoms through the triazole groups assists formation of heterobimetallic Ag(I)/V(V) secondary building blocks in a linear V-Ag-Ag-V sequence that is observed in complexes 2-4. These unprecedented tetranuclear {Ag(2)(VO(2)F(2))(2)(tr)(4)} units (the intermetal Ag-Ag and Ag-V distances are 4.24-4.36 and 3.74-3.81 Å, respectively), in which vanadium(V) oxofluoride units possess distorted trigonal bipyramidal environment {VO(2)F(2)N}¯, are incorporated into 1D ribbon (2) or 2D square nets (3, 4) using bitopic μ(4)-triazole ligands. The valence bond calculation for vanadium atoms shows +V oxidation state in the corresponding compounds. Thermal stability and photoluminescence properties were studied for all reported coordination polymers.
  Inorganic Chemistry 07/2012; 51(15):8025-33. · 4.60 Impact Factor
• Article: An isomorphous series of cubic, copper-based triazolyl isophthalate MOFs: linker substitution and adsorption properties.

  Jörg Lincke, Daniel Lässig, Merten Kobalz, Jens Bergmann, Marcel Handke, Jens Möllmer, Marcus Lange, Christian Roth, Andreas Möller, Reiner Staudt, Harald Krautscheid
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  ABSTRACT: An isomorphous series of 10 microporous copper-based metal-organic frameworks (MOFs) with the general formulas (∞)(3)[{Cu(3)(μ(3)-OH)(X)}(4){Cu(2)(H(2)O)(2)}(3)(H-R-trz-ia)(12)] (R = H, CH(3), Ph; X(2-) = SO(4)(2-), SeO(4)(2-), 2 NO(3)(2-) (1-8)) and (∞)(3)[{Cu(3)(μ(3)-OH)(X)}(8){Cu(2)(H(2)O)(2)}(6)(H-3py-trz-ia)(24)Cu(6)]X(3) (R = 3py; X(2-) = SO(4)(2-), SeO(4)(2-) (9, 10)) is presented together with the closely related compounds (∞)(3)[Cu(6)(μ(4)-O)(μ(3)-OH)(2)(H-Metrz-ia)(4)][Cu(H(2)O)(6)](NO(3))(2)·10H(2)O (11) and (∞)(3)[Cu(2)(H-3py-trz-ia)(2)(H(2)O)(3)] (12(Cu)), which are obtained under similar reaction conditions. The porosity of the series of cubic MOFs with twf-d topology reaches up to 66%. While the diameters of the spherical pores remain unaffected, adsorption measurements show that the pore volume can be fine-tuned by the substituents of the triazolyl isophthalate ligand and choice of the respective copper salt, that is, copper sulfate, selenate, or nitrate.
  Inorganic Chemistry 07/2012; 51(14):7579-86. · 4.60 Impact Factor
• Article: New organometallic single-source precursors for CuGaS(2)-polytypism in gallite nanocrystals obtained by thermolysis.

  Oliver Kluge, Dirk Friedrich, Gerald Wagner, Harald Krautscheid
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  ABSTRACT: The complex [((i)Pr(3)PCu)(2)(Me(2)Ga)(2)(SCH(2)CH(2)S)(2)] (4) was synthesized from trimethylgallium, [((i)Pr(3)PCu)(4)(SCH(2)CH(2)S)(2)] (1) and ethanedithiol by elimination of methane. The related monomethyl compound [((i)Pr(3)PCu)(2)(MeGaSPh)(2)(SCH(2)CH(2)S)(2)] (5) has been prepared from [((i)Pr(3)PCuSPh)(3)] (2) and [(MeGaSCH(2)CH(2)S)(2)] (3) by a ligand exchange reaction in tetrahydrofuran solution. The molecular structures of 1 and 3-5 were determined by single crystal X-ray diffraction. Thermolysis of 4 and 5 results in the formation of the ternary semiconductor CuGaS(2), gallite. The residue of 5 was characterized using X-ray powder diffraction, energy dispersive X-ray spectroscopy and transmission electron microscopy. The CuGaS(2) crystals obtained are mainly hexagonal plates of around 200 to 300 nm diameter and 10 to 30 nm thickness, exhibiting an unusual metastable hexagonal crystal structure, related to wurtzite. Partially, the usual tetragonal chalcopyrite structure or its disordered cubic zinc-blende analogue is realized by stacking faults, resulting in an overall similarity to the zinc-blende-wurtzite polytypism in ZnS and related compounds.
  Dalton Transactions 06/2012; 41(28):8635-42. · 3.84 Impact Factor
• Article: 1,2,4-Triazole functionalized adamantanes: a new library of polydentate tectons for designing structures of coordination polymers.

  Ganna A Senchyk, Andrey B Lysenko, Ishtvan Boldog, Eduard B Rusanov, Alexander N Chernega, Harald Krautscheid, Konstantin V Domasevitch
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  ABSTRACT: A series of functionalized adamantanes: 1,3-bis(1,2,4-triazol-4-yl)(tr(2)ad); 1,3,5-tris(1,2,4-triazol-4-yl)-(tr(3)ad); 1,3,5,7-tetrakis(1,2,4-triazol-4-yl)adamantanes (tr(4)ad) and 3,5,7-tris(1,2,4-triazol-4-yl)-1-azaadamantane (tr(3)ada) were developed as a new family of geometrically rigid polydentate tectons for supramolecular synthesis of framework solids. The coordination compounds were prepared under hydrothermal conditions; their structures reveal a special potential of the triazolyl adamantanes for the generation of highly-connected and open frameworks as well as structures based upon polynuclear metal clusters assembled with short-distance N(1),N(2)-triazole bridges. Complexes [Cd{L}(2)]A·nH(2)O [L = tr(3)ad, A = 2NO(3)(-) (4), CdCl(4)(2-) (5); L = tr(3)ada, A = CdI(4)(2-) (7)] are isomorphous and adopt a layered 3,6-connected structure of CdI(2) type. [{Cu(3)(OH)}(2)(SO(4))(5)(H(2)O)(2){tr(3)ad}(3)]·26H(2)O (6) is a layered polymer based upon Cu(3)(μ(3)-OH) nodes and trigonal tr(3)ad links. In [Cu(3)(OH)(2){tr(3)ada}(2)(H(2)O)(4)](ClO(4))(4) (8), [Cu(2){tr(3)ada}(2)(H(2)O)(3)](SO(4))(2)·7H(2)O (9) and [Cd(2){tr(3)ada}(3)]Cl(4)·28H(2)O (10) (UCl(3)-type net) the organic tripodal ligands bridge polynuclear metal clusters. Complexes [Ag{tr(4)ad}]NO(3)·3.5H(2)O (11) and [Cu{tr(4)ad}(H(2)O)](ClO(4))(2)·3H(2)O (12) have 3D SrAl(2)-type frameworks with the metal ions and adamantane tectons as topologically equivalent tetrahedral nodes, while in [Cd(3)Cl(6){tr(4)ad}(2)]·9H(2)O (13) the ligands bridge trinuclear six-connected Cd(3)Cl(6)(μ-tr)(4)(tr)(2) clusters. In the compounds [Cd(2){tr(2)ad}(4)(H(2)O)(4)](CdBr(4))(2)·2H(2)O (2) and [Cd{tr(2)ad}(4){CdI(3)}(2)]·4H(2)O (3) the bitopic ligands provide simple links between the metal ions, while in [Ag(2){tr(2)ad}(2)](NO(3))(2)·2H(2)O (1) the ligand is tetradentate and generates a 3D framework.
  Dalton Transactions 06/2012; 41(28):8675-89. · 3.84 Impact Factor
• Article: Trialkylphosphine-stabilized copper(I) gallium(III) phenylchalcogenolate complexes: crystal structures and generation of ternary semiconductors by thermolysis.

  Oliver Kluge, Harald Krautscheid
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  ABSTRACT: A series of organometallic trialkylphosphine-stabilized copper gallium phenylchalcogenolate complexes [(R(3)P)(m)Cu(n)Me(2-x)Ga(EPh)(n+x+1)] (R = Me, Et, (i)Pr, (t)Bu; E = S, Se, Te; x = 0, 1) has been prepared and structurally characterized by X-ray diffraction. From their molecular structures three groups of compounds can be distinguished: ionic compounds, ring systems, and cage structures. All these complexes contain one gallium atom bound to one or two methyl groups, whereas the number of copper atoms, and therefore the nuclearity of the complexes, is variable and depends mainly on size and amount of phosphine ligand used in synthesis. The Ga-E bonds are relatively rigid, in contrast to flexible Cu-E bonds. The lengths of the latter are controlled by the coordination number and steric influences. The Ga-E bond lengths depend systematically on the number of methyl groups bound to the gallium atom, with somewhat shorter bonds in monomethyl compounds compared to dimethyl compounds. Quantum chemical computations reproduce this trend and show furthermore that the rotation of one phenyl group around the Ga-E bond is a low energy process with two distinct minima, corresponding to two different conformations found experimentally. Mixtures of different types of chalcogen atoms on molecular scale are possible, and then ligand exchange reactions in solution lead to mixed site occupation. In thermogravimetric studies the complexes were converted into the ternary semiconductors CuGaE(2). The thermolysis reaction is completed at temperatures between 250 and 400 °C, typically with lower temperatures for the heavier chalcogens. Because of significant release of Me(3)Ga during the thermolysis process, and especially in case of copper excess in the precursor complexes, binary copper chalcogenides are obtained as additional thermolysis products. Quaternary semiconductors can be obtained from mixed chalcogen precursors.
  Inorganic Chemistry 06/2012; 51(12):6655-66. · 4.60 Impact Factor
• Article: Assessment of hydrogen storage by physisorption in porous materials

  Moises Bastos-Neto, Christin Patzschke, Marcus Lange, Jens Möllmer, Andreas Möller, Sven Fichtner, Christian Schrage, Daniel Lässig, Jörg Lincke, Reiner Staudt, Harald Krautscheid, Roger Gläser
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  ABSTRACT: As a basis for the evaluation of hydrogen storage by physisorption, adsorption isotherms of H2 were experimentally determined for several porous materials at 77 K and 298 K at pressures up to 15 MPa. Activated carbons and MOFs were studied as the most promising materials for this purpose. A noble focus was given on how to determine whether a material is feasible for hydrogen storage or not, dealing with an assessment method and the pitfalls and problems of determining the viability. For a quantitative evaluation of the feasibility of sorptive hydrogen storage in a general analysis, it is suggested to compare the stored amount in a theoretical tank filled with adsorbents to the amount of hydrogen stored in the same tank without adsorbents. According to our results, an “ideal” sorbent for hydrogen storage at 77 K is calculated to exhibit a specific surface area of >2580 m2 g−1 and a micropore volume of >1.58 cm3 g−1.
  Energy & Environmental Science 05/2012; 5:8294-8303. · 9.61 Impact Factor
• Article: Solid-state syntheses of coordination polymers by thermal conversion of molecular building blocks and polymeric precursors.

  Daniel Lässig, Jörg Lincke, Renata Gerhardt, Harald Krautscheid
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  ABSTRACT: The syntheses and crystal structures of a mononuclear cadmium complex and five novel coordination polymers based on 1,2,4-triazolyl benzoates are presented. The compounds (∞)(3)[Cd(H-Me-trz-pba)(2)] (2), (∞)(3)[Cd(Me-3py-trz-pba)(2)] (4), and (∞)(3)[Zn(H-Me-trz-pba)(2)] (6) can be obtained by solvothermal synthesis or simple heating of the starting materials in appropriate solvents, and are also accessible by thermal conversion of the complex [Cd(H-Me-trz-pba)(2)(H(2)O)(4)] (1), the one-dimensional (1D) coordination polymer (∞)(1)[Cd(Me-3py-trz-pba)(2)(H(2)O)(2)]·H(2)O (3), and the porous three-dimensional (3D) framework (∞)(3)[Zn(H-Me-trz-pba)2]·4H(2)O (5), respectively. The driving force for these conversions is the formation of thermally stable, nonporous, crystalline 3D coordination polymers. The structural transformations are accompanied by the loss of water and reveal significant changes of the coordination spheres of the metal ions caused by a rearrangement of the triazolyl benzoate ligands. Compounds 2, 4, 5, and 6 exhibit 4- and 5-fold interpenetration of diamondoid networks (dia) and are thermally stable up to 380 °C.
  Inorganic Chemistry 05/2012; 51(11):6180-9. · 4.60 Impact Factor
• Article: Facile access to a series of large polycondensed pyridazines and their utility for the supramolecular synthesis of coordination polymers.

  Konstantin V Domasevitch, Pavlo V Solntsev, Harald Krautscheid, Iryna S Zhylenko, Eduard B Rusanov, Alexander N Chernega
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  ABSTRACT: Domino cyclization of ketoenols and hydrazine leads to a series of polycondensed pyridazines, which reveal potential as rigid N-donor multidentate ligands for supramolecular synthesis of open coordination polymers.
  Chemical Communications 05/2012; 48(47):5847-9. · 6.17 Impact Factor
• Article: Pure and mixed gas adsorption of CH4 and N2 on the metal–organic framework Basolite® A100 and a novel copper-based 1,2,4-triazolyl isophthalate MOF

  Jens Möllmer, Marcus Lange, Andreas Möller, Christin Patzschke, Karolin Stein, Daniel Lässig, Jörg Lincke, Roger Gläser, Harald Krautscheid, Reiner Staudt
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  ABSTRACT: Pure gas adsorption isotherms of CH4 and N2 and their binary mixtures were measured at 273 K, 298 K and 323 K and up to 2 MPa on two different microporous metal–organic frameworks (MOFs), i.e. the commercially available Basolite® A100 and the recently reported copper-based triazolyl benzoate MOF 3∞[Cu(Me-4py-trz-ia)] (1). The Tòth isotherm model and the vacancy solution model were used to describe the experimentally determined isotherms and proved to be well suited for this purpose. While 1 shows a more homogeneous surface with a nearly constant isosteric heat of adsorption of 18–18.5 kJ mol−1 for CH4 and 12–15 kJ mol−1 for N2, the isosteric heat of adsorption at zero coverage for Basolite® A100 is 19 kJ mol−1 for CH4 and 16.2 kJ mol−1 for N2, decreasing significantly with increasing loading. Binary adsorption isotherms were measured gravimetrically to determine the total adsorbed mass of CH4 and N2. The van Ness method was successfully applied to calculate partial loadings from gravimetrically measured binary adsorption isotherms. Further studies by volumetric–chromatographic experiments support the good correlation between experimental data and predictions by the vacancy solution model (VSM-Wilson) and the ideal adsorbed solution theory (IAST) from pure gas isotherms. The experimental selectivities were determined to be αCH4/N2 = 4.0–5.0 for 1, slightly higher than for Basolite® A100 with αCH4/N2 = 3.4–4.5. These values are in good agreement with predictions for ideal selectivities based on Henry's law constants. From the experimental selectivities the potential of both MOFs in gas separation of CH4 from N2 can be derived.
  Journal of Materials Chemistry 03/2012; 22:10274-10286. · 5.97 Impact Factor
• Article: New organic-inorganic frameworks incorporating iso- and heteropolymolybdate units and a 3,3',5,5'-tetramethyl-4,4'-bi-1H-pyrazole-2,2'-diium multiple hydrogen-bond donor.

  Liliana V Lukashuk, Andrey B Lysenko, Harald Krautscheid, Konstantin V Domasevitch
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  ABSTRACT: Poly[bis(3,3',5,5'-tetramethyl-4,4'-bi-1H-pyrazole-2,2'-diium) γ-octamolybdate(VI) dihydrate], {(C(10)H(16)N(4))(2)[Mo(8)O(26)]·2H(2)O}(n), (I), and bis(3,3',5,5'-tetramethyl-4,4'-bi-1H-pyrazole-2,2'-diium) α-dodecamolybdo(VI)silicate tetrahydrate, (C(10)H(16)N(4))(2)[SiMo(12)O(40)]·4H(2)O, (II), display intense hydrogen bonding between the cationic pyrazolium species and the metal oxide anions. In (I), the asymmetric unit contains half a centrosymmetric γ-type [Mo(8)O(26)](4-) anion, which produces a one-dimensional polymeric chain by corner-sharing, one cation and one water molecule. Three-centre bonding with 3,3',5,5'-tetramethyl-4,4'-bi-1H-pyrazole-2,2'-diium, denoted [H(2)Me(4)bpz](2+) [N···O = 2.770 (4)-3.146 (4) Å], generates two-dimensional layers that are further linked by hydrogen bonds involving water molecules [O...O = 2.902 (4) and 3.010 (4) Å]. In (II), each of the four independent [H(2)Me(4)bpz](2+) cations lies across a twofold axis. They link layers of [SiMo(12)O(40)](4-) anions into a three-dimensional framework, and the preferred sites for pyrazolium/anion hydrogen bonding are the terminal oxide atoms [N···O = 2.866 (6)-2.999 (6) Å], while anion/aqua interactions occur preferentially via μ(2)-O sites [O···O = 2.910 (6)-3.151 (6) Å].
  Acta crystallographica. Section C, Crystal structure communications 12/2011; 67(Pt 12):m378-83. · 0.78 Impact Factor
• Source

  Available from: Anusree Viswanath

  Article: A novel Zn(4)O-based triazolyl benzoate MOF: synthesis, crystal structure, adsorption properties and solid state 13C NMR investigations.

  Jörg Lincke, Daniel Lässig, Karolin Stein, Jens Moellmer, Anusree Viswanath Kuttatheyil, Christian Reichenbach, Andreas Moeller, Reiner Staudt, Grit Kalies, Marko Bertmer, Harald Krautscheid
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  ABSTRACT: The newly synthesized Zn(4)O-based MOF (3)(∞)[Zn(4)(μ(4)-O){(Metrz-pba)(2)mPh}(3)]·8 DMF (1·8 DMF) of rare tungsten carbide (acs) topology exhibits a porosity of 43% and remarkably high thermal stability up to 430 °C. Single crystal X-ray structure analyses could be performed using as-synthesized as well as desolvated crystals. Besides the solvothermal synthesis of single crystals a scalable synthesis of microcrystalline material of the MOF is reported. Combined TG-MS and solid state NMR measurements reveal the presence of mobile DMF molecules in the pore system of the framework. Adsorption measurements confirm that the pore structure is fully accessible for nitrogen molecules at 77 K. The adsorptive pore volume of 0.41 cm(3) g(-1) correlates well with the pore volume of 0.43 cm(3) g(-1) estimated from the single crystal structure.
  Dalton Transactions 11/2011; 41(3):817-24. · 3.84 Impact Factor
• Article: A microporous copper metal-organic framework with high H2 and CO2 adsorption capacity at ambient pressure.

  Daniel Lässig, Jörg Lincke, Jens Moellmer, Christian Reichenbach, Andreas Moeller, Roger Gläser, Grit Kalies, Katie A Cychosz, Matthias Thommes, Reiner Staudt, Harald Krautscheid
  Angewandte Chemie International Edition 09/2011; 50(44):10344-8. · 13.45 Impact Factor
• Article: Trialkylphosphine-stabilized copper(I) phenylchalcogenolate complexes--crystal structures and copper-chalcogenolate bonding.

  Oliver Kluge, Katharina Grummt, Ralf Biedermann, Harald Krautscheid
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  ABSTRACT: A series of trialkylphosphine-stabilized copper(I) phenylchalcogenolate complexes [(R(3)P)(m)(CuEPh)(n)] (R = Me, Et, (i)Pr, (t)Bu; E = S, Se, Te) has been prepared and structurally characterized by X-ray diffraction. Structures were found to be mono-, di-, tri-, tetra-, hexa-, hepta-, or decanuclear, depending mainly on size and amount of phosphine ligand. Several structural details were observed, including unusually long Cu-E bonds or secondary Cu-E connections, μ(4)-bridging, and planar bridging chalcogenolate ligands. Relatively rigid Cu-E-C angles were found to be of significant influence on the flexible molecular structures, especially for bridging chalcogenolate ligands, since in these cases a correlation results between the Cu-E-Cu angles and the inclination of the E-C bonds to their Cu-E-Cu planes. We further address some of these phenomena by means of density functional computations.
  Inorganic Chemistry 06/2011; 50(11):4742-52. · 4.60 Impact Factor
• Article: Self-assembly hexanuclear metallacontainer hosting halogenated guest species and sustaining structure of 3D coordination framework.

  Evgen V Govor, Andrey B Lysenko, David Quiñonero, Eduard B Rusanov, Alexander N Chernega, Jens Moellmer, Reiner Staudt, Harald Krautscheid, Antonio Frontera, Konstantin V Domasevitch
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  ABSTRACT: Chloride-centered hexanuclear hydroxopyrazolate reveals potential as a receptor of halomethane and halometallate species and as a molecular building block for coordination polymers.
  Chemical Communications 02/2011; 47(6):1764-6. · 6.17 Impact Factor
• Article: Synthesis, crystal structure, and electron paramagnetic resonance investigations of heteronuclear Co(II)/Zn(II) and Co(II)/Cd(II) coordination polymers.

  Daniel Lässig, Jörg Lincke, Jan Griebel, Reinhard Kirmse, Harald Krautscheid
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  ABSTRACT: The crystal structures of five new Co(II), Zn(II), and Cd(II) coordination polymers based on pyridine-substituted triazolyl carboxylates are reported. The two isomorphous compounds (∞)³[M(Me-3py-pba)₂] (M = Zn, Co) possess {6⁶} topology (dia). In order to obtain heteronuclear compounds, we synthesized Co(II)-substituted Zn(II) and Cd(II) coordination polymers. At T = 5 K, the powder samples of the diamagnetically diluted Co(II)/Zn(II) and Co(II)/Cd(II) systems [Co/(Zn,Cd) ≈ 0.01] show intense electron paramagnetic resonance spectra, which were analyzed with an effective spin of S' = ½. The g tensor as well as the ⁵⁹Co hyperfine tensor A(Co) are strongly anisotropic. The g tensor components are used to gain information about the symmetry of the Co(II) coordination sphere and covalency effects. Differential thermal analysis/thermogravimetry-mass spectrometry and temperature-dependent powder X-ray diffraction studies reveal high thermal stability of the three-dimensional coordination polymers up to 390 °C.
  Inorganic Chemistry 01/2011; 50(1):213-9. · 4.60 Impact Factor
• Article: “Fluoride molecular scissors”: A rational construction of new Mo(VI) oxofluorido/1,2,4-triazole MOFs

  Ganna A. Senchyk, Andrey B. Lysenko, Harald Krautscheid, Konstantin V. Domasevitch
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  ABSTRACT: New molybdenum(VI) oxofluoride-organic hybrids, [Mo2F2O5(tr2ad)] (1) and [Mo2F2O5(tr2ad2)] (2), supported by angular or linear N1,N2-(1,2,4-triazol-4-yl) bridges (tr2ad, 1,3-bis(1,2,4-triazol-4-yl)adamantane; tr2ad2, 3,3′-bis(1,2,4-triazol-4-yl)-1,1′-biadamantane), were prepared in an aqueous HF solution under hydrothermal conditions. The structure of the compounds includes dinuclear corner-sharing {Mo2F2O5} cores, in which two octahedral Mo ions are linked by one oxygen atom (Mo-O 1.90–1.92 Å) and two triazolyl groups (Mo-N 2.37–2.40 Å). The latter occupy the cis-positions in the {Mo2F2O5(tr)2} coordination clusters (“secondary building blocks”). Terminal fluoride and two “molybdenyl” oxygen atoms complete the coordination sphere of each molybdenum ions. In both cases the ligands show the maximal tetradentate mode connecting the adjacent inorganic units into a zigzag chain.
  Inorganic Chemistry Communications 01/2011; 14(9):1365-1368. · 1.97 Impact Factor
• Article: Synthesis, Crystal Structure, and Electron Paramagnetic Resonance Investigations of Heteronuclear CoII/ZnII and CoII/CdII Coordination Polymers

  Daniel Lässig, Jörg Lincke, Jan Griebel, Reinhard Kirmse, Harald Krautscheid
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  ABSTRACT: The crystal structures of five new CoII, ZnII, and CdII coordination polymers based on pyridine-substituted triazolyl carboxylates are reported. The two isomorphous compounds ∞3[M(Me-3py-pba)2] (M = Zn, Co) possess {66} topology (dia). In order to obtain heteronuclear compounds, we synthesized CoII-substituted ZnII and CdII coordination polymers. At T = 5 K, the powder samples of the diamagnetically diluted CoII/ZnII and CoII/CdII systems [Co/(Zn,Cd) ≈ 0.01] show intense electron paramagnetic resonance spectra, which were analyzed with an effective spin of S′ = 1/2. The g tensor as well as the 59Co hyperfine tensor ACo are strongly anisotropic. The g tensor components are used to gain information about the symmetry of the CoII coordination sphere and covalency effects. Differential thermal analysis/thermogravimetry−mass spectrometry and temperature-dependent powder X-ray diffraction studies reveal high thermal stability of the three-dimensional coordination polymers up to 390 °C.
  11/2010;