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  • Single-Molecule Magnet and Magnetothermal Properties of Two-Dimensional Polymers Containing Heterometallic [Cu5Ln2] (Ln = GdIII and DyIII) Motifs
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-19
    Vadapalli Chandrasekhar, Atanu Dey, Sourav Das, María Palacios, Enrique Colacio

    The reaction of a compartmental ligand N,N′-bis(3-methoxysalicylidene)-1,3-diamino-2-propanol (H3L), with CuII and LnIII salts under solvothermal conditions afforded two-dimensional coordination polymers, [{Cu5Gd2(L)2(µ3-OH)4(NO3)4(µ-OH2)2}(NO3)2]∞ (1) and [{Cu5Dy2(L)2(µ3-OH)4(NO3)4(MeOH)2}(NO3)2]∞ (2). Detailed study of the magnetic properties of the two coordination polymers reveals that the [Cu5Dy2]analogue shows SMM behavior with an energy barrier of ~12 K with τ0 = 10-6 s under zero-dc field while the [Cu5Gd2] analogue showed magneto-caloric effect with ΔSm value of 17.55 J kg-1 K-1 at T = 2 K (H = 5 T). Interestingly, the magnetic and SMM properties of the previously reported molecular and one-dimensional analogues containing the [Cu5Ln2] motif are preserved even in the twodimensional coordination networks.

    更新日期:2018-01-19
  • Front Cover: Synthetic High-Valent M–O–X Oxidants (Eur. J. Inorg. Chem. /2018)
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-19
    Paolo Pirovano, Aidan R. McDonald
    更新日期:2018-01-19
  • Ruthenium(II)-(p-cymene)-N-Heterocyclic Carbene Complexes for the N-Alkylation of Amine Using the Green Hydrogen Borrowing Methodology
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-18
    İsmail Özdemir, Murat Kaloğlu, Nevin Gürbüz, David Semeril

    Six ruthenium(II) complexes with the general molecular formula [RuCl2(NHC)(η6-p-cymene)] (NHC = N-heterocyclic carbene) were synthesized by the transmetalation method from [RuCl2(η6-p-cymene)]2 and silver(I)-NHC complexes. All complexes were fully characterized by analytical and spectral methods (FT-IR, elemental analysis and 1H and 13C NMR). The solid-state structure of one of the ruthenium complexes {dichloro-[1-(2-(2-ethoxyphenoxy)ethyl)-3-(3,5-dimethylbenzyl)benzimidazol-2-ylidene](p-cymene) ruthenium(II)} has been established by single-crystal X-ray diffraction study, which revealed that the ruthenium atom adopt a classical piano-stool coordination geometry. Under the optimised conditions, these ruthenium complexes were found to be efficient catalysts for N-alkylation of aniline with arylmethyl alcohols using the hydrogen borrowing strategy, which is a cost-effective and environmentally attractive reaction for the preparation of N-alkylated amines.

    更新日期:2018-01-18
  • Influence of phase composition of bulk tungsten-vanadium oxides on the one-pot synthesis of acrylic acid from glycerol
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-17
    Daniel Delgado, Alessandro Chieregato, Maria Dolores Soriano, Elena Rodríguez-Aguado, Lidia Ruiz-Rodríguez, Enrique Rodríguez Castellón, José M. López Nieto

    A series of W-V-O catalysts which present different m-WO3 and h-WO3 phase contents were hydrothermally synthesized employing different tungsten, vanadium and ammonium precursors. Characterization of these materials was carried out by several physicochemical techniques such as powder X-Ray diffraction, N2-adsorption, SEM, XEDS, TG, Raman, FT-IR spectroscopy, TPD-NH3 and XPS. Finally, acid-redox properties were analyzed using methanol aerobic transformation as a characterization reaction. A correlation between phase composition as well as acid- and redox- properties was observed, which were correlated to the catalytic performance of the titled materials in the one-pot glycerol oxydehydration reaction. The monoclinic m-WO3 phase shows a concentration of acid sites significantly lower than that of the hexagonal tungsten bronze, h-WO3, making acid properties of W-V-O oxides directly related to the presence of h-WO3 crystals. The presence of a higher concentration of acid sites in V-containing h-WO3 crystals is a key factor to achieve high selectivity to both acrolein and acrylic acid during the one-pot glycerol oxydehydration. Also, V-sites in h-WO3 present higher selectivity in the consecutive reaction (acrolein partial oxidation to acrylic acid), while V-sites in m-WO3 phase fundamentally lead to the formation of carbon oxides.

    更新日期:2018-01-17
  • Facile Silylation of Cyclitols Using Silyl Bis(triflates)
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-17
    Anke Topp, Martin Köckerling, Helmut Reinke, Ralf Miethchen, Constantin Mamat

    Novel silylated diols and polyols were prepared using a recently developed synthesis route with bifunctionalized silyl triflates. These silyl derivatives include two triflate functions which allow a selective protection of two hydroxyl groups. Moreover, the conformation of the silyl chain in the silane backbone led to exceptional UV properties.

    更新日期:2018-01-17
  • Redox-isomerism in main group chemistry: tin complex with o-iminoquinone ligands
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-17
    Maxim Chegerev, Alexandr Vladimirovich Piskunov, Alyona Starikova, Stanislav Kubrin, Georgy Fukin, Vladimir Cherkasov, Gleb Abakumov

    Bis-chelate tin complex 1 on the basis of 4,6-di-tert-butyl-N-(tert-butyl)-ortho-aminophenol ligand representing the first example of redox-isomeric compound in main group chemistry was synthesized and characterized by X-ray analysis. It was found that 1 exists in two electromeric forms in non-polar solvents: diamagnetic pseudotetrahedral (AP)2SnIV (1a) and paramagnetic tetragonal-pyramidal structure of low-valence tin (imSQ)2SnII (1b) (where AP and imSQ - dianion and radical-anion forms of the ligand, respectively). The reversible redox-isomeric rearrangement between 1a and 1b was investigated in solution by means of magnetochemistry, EPR, UV-Vis and 119Sn Mössbauer spectroscopy. This interconversion can be quenched by an addition of strong donor ligand such as pyridine (Py), resulting in an octahedral complex (AP)2SnIV(Py)2 (2) which does not undergo redox-isomerism.

    更新日期:2018-01-17
  • Zinc Ferrite Anchored Multiwalled Carbon Nanotubes for High-Performance Supercapacitor Applications
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-17
    Shrikant S. Raut, Babasaheb R. Sankapal, Md. Shahriar A. Hossain, Subrata Pradhan, Rahul R. Salunkhe, Yusuke Yamauchi
    更新日期:2018-01-17
  • One-Pot Synthesis of Highly Fluorescent Carbon Dots from Spinach and Multipurpose Applications
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-17
    Guojuan Ren, Mingyu Tang, Fang Chai, Hongbo Wu
    更新日期:2018-01-17
  • Synthesis, crystal and electronic structure of the novel titanium bismuthides Sr5Ti12Bi19+x, Ba5Ti12Bi19+x, and Sr5-δEuδTi12Bi19+x (x ≈ 0.5-1.0; δ ≈ 2.4, 4.0)
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-16
    Alexander Ovchinnikov, Svilen Bobev

    Crystals of the new ternary bismuthides AE5Ti12Bi19+x (AE = Sr, Ba) and Sr5-δEuδTi12Bi19+x (δ ≈ 2.4, 4.0; x <= 1.0) were grown using an excess of molten Bi as a flux. The title compounds crystallize in the cubic non-centrosymmetric space group P-43m and are structurally related to the antimonides Ba5M12Sb19+x (M = Ti, V, Nb). The crystal structure features Ti atoms stuffed in the γ-brass-like sub-lattice made of AE (AE = Sr, Ba, Eu) and Bi atoms. The arrangement of the AE atoms, on its own, represents a framework consisting of interconnected regular tetrahedra and octahedra. Another notable attribute of the AE5Ti12Bi19+x structure is the disordered Bi moiety located at the center of the unit cell and showing homoatomic Bi-Bi bonding. Electronic structure calculations and electrical resistivity measurements indicate metallic behavior of the new bismuthides. Magnetization measurements on samples of Sr5-δEuδTi12Bi19+x show paramagnetic behavior consistent with the 2+ ground state for Eu. The measurements also confirm no magnetic ordering down to 3 K, stemming from the geometrically frustrated exchange interactions of the Eu2+ cations.

    更新日期:2018-01-16
  • Coordination of 3-methylindole-based tripodal tetraphosphine ligands to iron(+II), cobalt(+II) and nickel(+II) and investigations of their subsequent two-electron-reduction
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-16
    Fenna van de watering, Wowa Stroek, Jarl Ivar van der Vlugt, Bas de Bruin, Wojciech Dzik, Joost Reek

    We report the coordination chemistry of indole based tripodal tetraphosphine ligands to iron(II), cobalt(II) and nickel(II). These complexes are formed by simple synthetic protocols and were characterized by a combination of spectroscopic techniques and single crystal X-ray analysis. The molecular structures as determined by X-ray diffraction show that the geometry of the nickel and cobalt complexes are distorted trigonal bipyrimidal. The monocationic iron(II) complexes also have a distorted trigonal bipyrimidal geometry, but the dicationic analogue has an octahedral geometry. Two-electron-reduction of the cobalt(+II) and the nickel(+II) complex in the presence of N2 did not lead to the coordination of N2. In contrast, two-electron-reduction of the iron(+II) complexes did lead to coordination of dinitrogen to the iron centre. The Fe(0)N2L1H complex has a trigonal bipyrimidal geometry, and the NN bond distance of the coordinated dinitrogen ligand is longer than that of free dinitrogen, indicating that coordination to this iron(0) complex results in activation of the NN bond.

    更新日期:2018-01-16
  • Histaminol and its complexes with copper(II) - studies in solid state and solution
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-16
    Piotr Maślewski, Dariusz Wyrzykowski, Maciej Witwicki, Anna Dołęga

    Histaminol (4(5) (β-hydroxyethyl)imidazole, 4-(1H-Imidazol-2-yl)ethanol, L) is an analogue of histamine and its minor metabolite. So far its properties have not been studied in detail due to the synthetic difficulties. Here the structure and acid-base properties of histaminol as well as the results of studies on its copper(II) complexes in solid state and aqueous solution are reported. Stability constants of the histaminol - Cu(II) system are measured and each stage of the complex formation is illustrated with the relevant crystal structure and the EPR spectrum.

    更新日期:2018-01-16
  • A Novel Hexanuclear Cd-MOF Exhibiting Dual Mechanisms-triggering Fluorescence Quenching Response toward Fe3+ Ions in DMF
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-16
    Ying-Hui Zhang, Long-Sheng Li, Xi Wang, Yan-Yuan Jia, Shi-Xian Xu, Mei-Hui Yu

    A novel hexanuclear Cd(II) metal-organic framework (1) based on 4-(1H-Pyrazole-4-carboxamido) benzonic acid (H2L) has been synthesized, featuring a three dimensional microporous framework. Notably, 1 shows a unique fluorescence quenching response toward Fe3+ with high selectivity and sensitivity (Stern-Volmer constant KSV = 2.07 × 104 M-1), attributable to the coaction of absorption competition and energy transfer (ET) mechanism. Further spectral analysis indicates that energy transfer mechanism contribute dominantly to the fluorescent quenching of 1.

    更新日期:2018-01-16
  • Yann Garcia
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-16
    更新日期:2018-01-16
  • Development of Efficient Copper-Based MOF-Derived Catalysts for the Reduction of Aromatic Nitro Compounds
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-15
    Özlem Karahan, Emre Biçer, Adnan Taşdemir, Alp Yürüm, Selmiye Alkan Gürsel

    Two Copper-based Cu3(btc)2 and Cu(Im)2 metal-organic frameworks were synthesized and annealed to form nanoporous Cu/Cu2O@C and Cu@N-C nanoparticles for utilization as catalysts in the reduction reaction of aromatic nitro compounds to aromatic amines. All synthesized MOF compounds and MOF-derived nanoparticles were characterized using XRD, Raman, TGA, SEM-EDX and XPS methods. Also, the pore size distribution and surface area of the MOF-derived Cu/Cu2O@C and Cu@N-C nanoparticles were characterized by BJH and BET methods. After characterization, the catalysts Cu/Cu2O@C and Cu@N-C were catalytically tested for the reduction reactions of various aromatic nitro compounds chemically by monitoring via a UV-vis spectrometer. Both catalysts exhibited remarkable results compared with those in the literature. Also, the Cu/Cu2O@C catalyst showed better results than the Cu@N-C catalyst.

    更新日期:2018-01-15
  • Self-assembly of a Pd4L8 Double-walled Square Partly Takes Place through the Formation of Kinetically Trapped Species
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-15
    Tomoki Tateishi, Wenchao Zhu, Leonardo Hayato Foianesi-Takeshige, Tatsuo Kojima, Kazuho Ogata, Shuichi Hiraoka

    The self-assembly process of a Pd4L8 double-walled square (DWS), which was investigated by QASAP (quantitative analysis of self-assembly process), is quite different from that of single-walled macrocycles. DWS is assembled mainly through three pathways, with transient production of a kinetically trapped Pd3L6 double-walled triangle (DWT) and 200-nm-sized large intermediates. The change in the self-assembly pathway would arise from the difference in the flexibility of ditopic ligands. It was found that the leaving ligand, which is not a component of the final self-assembly, is essential for the formation of DWS in two of the self-assembly pathways.

    更新日期:2018-01-15
  • Group 11 Metal Complexes Coordinated by (Nitronyl Nitroxide)-2-ide Radical Anion: Facile Oxidation of Stable Radicals Controlled by MetalCarbon Bonds in Radical-Metalloids
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-15
    Keiji Okada, Ryu Tanimoto, Kiyomi Yamada, Shuichi Suzuki, Masatoshi Kozaki

    A series of group 11 metal complexes coordinated by (nitronyl nitroxide)-2-ide radical anions (NNM(dtpb) (NN: nitronyl nitroxide; M: Cu(I), Ag(I), and Au(I); dtpb: 1,2-bis(di-2-tolylphosphino)benzene)) was prepared. Their structures, electrochemical properties, and related theoretical calculations were investigated. The oxidation potential (Eox, V vs Fc/Fc+) of the NN-moiety in these radical-metalloids significantly shifted to the negative direction in comparison to that of the unsubstituted nitronyl nitroxide (NNH, Eox=+0.38 V) and strongly depended on the metal ion (Eox=-0.37 V for M=Cu(I), -0.31 V for Ag(I), and -0.28 V for Au(I)). The Eox values correlated with the energy level of the HOMO (SOMO) and also with the natural atomic charge of the C2 carbon atom attached to the metal ion, indicating that the ionic character of the metal-C2-carbon bond is a key factor in controlling the oxidation potential of these radical metalloids.

    更新日期:2018-01-15
  • The Nature of the Technetium Species Formed During the Oxidation of Technetium Dioxide with Oxygen and Water.
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-15
    Bradley Childs, Keith V. Lawler, Henrik Braband, Daniel S. Mast, Laurent Bigler, Urs Stalder, Derek R. Peterson, Alek Jansen, Paul M. Forster, Kenneth R. Czerwinski, Roger Alberto, Alfred P. Sattelberger, Frederic Poineau

    The oxidation of TcO₂ with O₂ in the presence of H₂O at 250 °C was investigated; Tc₂O₇ and a red product were observed after the reaction. UV-visible spectroscopy and cerium titration on the 'red' product are consistent with the presence of a reduced Tc species. It is proposed that the 'red' product was formed by the hydrolysis of Tc₂O₇ to HTcO₄ followed by the reduction of HTcO₄. The reaction products of TcO₂ with O₂/H₂O at 250 °C were also studied by mass spectrometry. The main dinuclear species were Tc₂O₇ and Tc₂O₅, while the main mononuclear species were TcO₃ and HTcO₄. The compound HTcO4 and associated hydrates were simulated to identify candidate structures for the 'red' product; however, neither the acid nor any related hydrates exhibited the UV-Visible signature of the 'red' product.

    更新日期:2018-01-15
  • Syntheses, structures, and magnetic properties of two series of 3d-4f heterometallic coordination polymers derived from pyrazine-2,3-dicarboxylic acid
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-14
    Ju-Wen Zhang, Yu-Ning Ren, Jia-Xuan Li, Bin-Qiu Liu, Yan-Ping Dong

    Twenty 3d-4f heterometallic coordination polymers (CPs), namely, [Ln2Co(2,3-pzdc)4(H2O)6]*2H2O [Ln = La (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Tb (7)], [Ln2Co(2,3-pzdc)4(H2O)4]*4H2O [Ln = Dy (8), Er (9)], [Ln2Cu(2,3-pzdc)4(H2O)6]*2H2O [Ln = La (10), Pr (11), Nd (12), Sm (13), Eu (14), Gd (15), Tb (16)], Dy2Cu(2,3-pzdc)4(H2O)4]*4H2O (17), and [Ln2Cu(2,3-pzdc)4(H2O)4]*2H2O [Ln = Er (18), Yb (19), Lu (20)], were synthesized successfully by the reactions of 2,3-H2pzdc with LnCl3*nH2O/Ln(NO3)3*nH2O and Co(NO3)2*3H2O/CuCl2*2H2O under hydrothermal conditions. CPs 1−20 are isostructural, and only the coordination and interstitial water molecules as well as the coordination numbers of Ln(III) are different from each other. In 1−20, the 2,3-pzdc anions link the Co(II)/Cu(II) and Ln(III) ions by two types of coordination modes to form a three-dimensional (3D) framework with a 3,3,4,4-connected (4*62)2(42*62*82)(63)2(65*8)2 topology. CPs 6 and 7 manifest the weak ferromagnetic interactions between Co(II) and Ln(III) in the low-temperature range. CP 8 exhibits a field-induced slow magnetic relaxation behavior. CP 16 shows a magnetic transition between short-range ferromagnetic ordering at 60 K and long-range ferromagnetic ordering below 26 K. CP 17 displays a field-induced single-molecule magnet (SMM) behavior with a Ueff value of 102.4 K.

    更新日期:2018-01-15
  • Synthetic High-Valent M–O–X Oxidants
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-15
    Paolo Pirovano, Aidan R. McDonald
    更新日期:2018-01-15
  • Front Cover: H-Mediated Magnetic Interactions between Layers in a 2D MnII–Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations (Eur. J. Inorg. Chem. /2018)
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-15
    Béatrice Gillon, Albert Hammerschmied, Arsen Gukasov, Alain Cousson, Thomas Cauchy, Eliseo Ruiz, John A. Schlueter, Jamie L. Manson
    更新日期:2018-01-15
  • H-Mediated Magnetic Interactions between Layers in a 2D MnII–Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-15
    Béatrice Gillon, Albert Hammerschmied, Arsen Gukasov, Alain Cousson, Thomas Cauchy, Eliseo Ruiz, John A. Schlueter, Jamie L. Manson
    更新日期:2018-01-15
  • Cover Feature: Cyanido-Bridged FeII–MI Dimetallic Hofmann-Like Spin-Crossover Coordination Polymers Based on 2,6-Naphthyridine (Eur. J. Inorg. Chem. /2018)
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-15
    Lucía Piñeiro-López, Francisco Javier-Valverde-Muñoz, Maksym Seredyuk, Carlos Bartual-Murgui, M. Carmen Muñoz, José Antonio Real
    更新日期:2018-01-15
  • Cover Feature: Design of Magnetic Coordination Polymers Built from Polyoxalamide Ligands: A Thirty Year Story (Eur. J. Inorg. Chem. /2018)
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-15
    Yves Journaux,, Jesús Ferrando-Soria, Emilio Pardo, Rafael Ruiz-Garcia, Miguel Julve, Francesc Lloret, Joan Cano, Yanling Li, Laurent Lisnard, Pei Yu, Humberto Stumpf, Cynthia L. M. Pereira
    更新日期:2018-01-15
  • Tetrahydrosalen Uranyl(VI) Complexes: Crystal Structures and Solution Binding Study
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-14
    Xiao Zhao, Di Zhang, Yu Ren, Shunsen Chen, Dahui Zhao

    A pair of uranyl complexes incorporating tetrahydrosalen and N,N-dimethyltetrahydrosalen ligands are synthesized and studied. Compared to the prototype Schiff-base (salen) structure, these new ligands with saturated secondary and tertiary amines exhibit higher chemo-stability, especially under acidic conditions. As shown by the X-ray crystallography, the coordination geometry of uranium in these new complexes is a distorted pentagonal bipyramid, with the (dimethyl)tetrahydrosalen wrapped around the equatorial plane of UO22+. Interestingly, UO2(H2[H4]salen) comprising the tetrahydrosalen ligand forms a dimer structure in the crystals, with two subunits held together by sharing one of the two phenoxy oxygen atoms from each subunits. Whereas, UO2([H2Me2]-salen) with the N,N-dimethyltetrahydrosalen ligand is in the monomer state, with a solvent molecule coordinated to uranium to complete the penta-coordination configuration. Moreover, as revealed by the UV−vis spectrometry using the colorimetry method, these hydrogenated salen ligands exhibited comparable or even higher binding affinity toward uranyl than the prototype Schiff-base salen ligand in weakly basic solution.

    更新日期:2018-01-15
  • HP-CaSiN2 - A New High-Pressure Modification
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-12
    Cordula Braun, Helmut Ehrenberg, Wolfgang Schnick

    HP-CaSiN2 was obtained by HP/HT-synthesis utilizing the multianvil technique (4.5 to 18 GPa, 900 to 1200 °C) starting from the ambient pressure phase CaSiN2. Structure solution and Rietveld refinement were started with the cell parameters of HP-CaSiN2 determined by selected area electron diffraction (SAED). The crystal structure of the high-pressure phase was refined in space group Pbca (no. 61) with a = 5.1296(2), b =10.2993(2), c = 14.5442(3) Å, V = 768.39Å3, Z = 16, RBragg = 0.0484, Rw= 0.0256 and GoF = 1.0. HP-CaSiN2 is built up by a three-dimensional nitridosilicate network of vertex-sharing SiN4-tetrahedra with N[2] bridging. The arrangement of the vertex linked tetrahedra in HP-CaSiN2, being isostructural with KGaO2, is a tilting distortion of the stuffed β-cristobalite type framework. Due to the high-pressure the tilting angle of the SiN4-tetrahedra has become much smaller so that the latter appear edge-sharing sharing which is only a consequence of the chosen view along [100]. The Ca-ions are located within these sechser-ring channels and are coordinated by 6 and 7 N-atoms, respectively. HP-CaSiN2 is similar to CaSiN2, but differs clearly in the rotation of the SiN4-tetrahedra and in the conformation of the sechser-rings. Because of their coexistence HP-CaSiN2 and CaSiN2 represent a very good example of an isosymmetric polymorphism.

    更新日期:2018-01-13
  • Improved Synthesis of Unsymmetrical N-aryl-N'-alkylpyridyl ß-Diketimines using Molecular Sieves and their Lithium Complexes
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-12
    Kuldeep Chand, Chen-Long Tsai, Hsuan-Ying Chen, Wei-Min Ching, Sung-Po Hsu, James R. Carey, Sodio Chin Neng Hsu

    The synthesis of unsymmetrical β-diketimines with N-aryl-N'-alkyl substitution require at least two condensation steps and tedious purification procedures. An improvement for the preparation of four unsymmetrical N-aryl-N'-alkylpyridyl β-diketimine ligands (HL1-HL4) using 5 Å molecular sieves was reported. Synthesis of four Li complexes (LiL1, LiL2, LiL3, and LiL4) containing N-aryl-N'-alkylpyridyl β-diketimines ligands is also presented. All four Li complexes were fully characterized by 1H NMR, 13C NMR, and elemental analysis. X-ray structure analysis and spectroscopic results indicate that the Li β-diketimine structures and ligand binding modes are governed by the bulkiness of the N-aryl substituent and the length of pyridyl arm of the N-aryl-N'-alkyl β-diketiminate ligand.

    更新日期:2018-01-12
  • Dispersion Makes a Difference - The Solid-State Structure of Hg[N(SiMe3)2]2
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-11
    Jonas Bresien, Christian Hering-Junghans, Peter Kumm, Axel Schulz, Max Thomas, Alexander Villinger

    The solid-state structure and Raman spectrum of Wannagat's mercurane, Hg[N(SiMe3)2]2 (1), are reported. Crystals were grown from the pure substance by slow cooling to −24 °C. Compound 1 crystallizes in the monoclinic space group P21/c as discrete monomers, which do not display intermolecular mercurophilic interactions. The molecular structure features a nearly linear N-Hg-N scaffold, while the (Me3Si)2N groups are in a staggered conformation with a dihedral angle of 116° to each other. This can be attributed to intramolecular dispersion interactions according to DFT calculations.

    更新日期:2018-01-11
  • A novel carbon quantum dots/porous InVO4 microsphere composite with enhanced photocatalytic activity
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-10
    qianhong shen, Zengyu You, Yang Yu, Tian Qin, Yuxuan Su, Hui Wang, Chunchun Wu, Fang Zhang, Hui Yang

    A novel carbon quantum dots/porous InVO4 (CQDs/p-InVO4) microsphere composite was synthesized through a facile reflux method. The relationship of structure and property of CQDs/p-InVO4 was studied in detail. The results show that as-prepared composites maintain the porous structure of p-InVO4 microsphere, while CQDs are uniformly loaded on the surface of p-InVO4 microsphere with an intimate interface. With this unique structure, the as-obtained samples exhibit enhanced photocatalytic degradation ability towards RhB under visible-light irradiation. The synergistic effect of more active sites, increased visible-light absorption and high separation efficiency of photo-generated electron-hole pairs is believed to be the reason for the enhanced photocatalytic activity.

    更新日期:2018-01-10
  • Synthesis of symmetric and non-symmetric Ni(II) thiophosphinito PECSP (E = S, O) pincer complexes and applications in Kumada coupling under mild conditions
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-10
    Patrick Hasche, Markus Joksch, Georgia Vlachopoulou, Hemlata Agarwala, Anke Spannenberg, Torsten Beweries

    The reaction of 1,3-dimercaptobenzene with iPr2PCl in the presence of the base NaH, furnishes the symmetric ligand [C6H4-1,3-(SPiPr2)2] (1a). The direct reaction of this ligand as well as of the literature-known non-symmetric ligand [C6H4-1-(SPiPr2)-3-(OPiPr2)] (1b) with NiCl2 affords the symmetric bis(thiophosphinito) PSCSP pincer complex [{C6H3-2,6-(SPiPr2)2}NiCl] (2a) as well as the phosphinito-thiophosphinito POCSP pincer complex [{C6H3-2-(SPiPr2)-6-(OPiPr2)}NiCl] (2b). Both complexes were fully characterized and their catalytic performance in Kumada coupling of aryl halides and p-tolyl magnesium bromide under mild conditions was evaluated.

    更新日期:2018-01-10
  • Synthesis of N-Doped Core-Shell-Structured porous CoSe@C Composites and Their Efficient Catalytic Activity for the Reduction of 4-nitrophenol
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-09
    Haoyang Zhao, Yunhui Li, Dongsheng Wang, Lang Zhao

    In this work, core-shell-structured CoSe@C and N-CoSe@C dodecahedra were successfully obtained by calcination from cobalt-based metal-organic frameworks (ZIF-67: Co-based MOFs or N-ZIF-67: N-containing ZIF-67), in this approach, the cobalt species in the ZIF-67 or N-ZIF-67 could react with selenium (Se) powder to form CoSe nanoparticles in situ, and translating the organic species into carbon material at temperatures between 700 and 900 °C for 2 h under nitrogen atmosphere, the as-synthesized materials were used for the reduction of 4-nitrophenol (4-NP) assisted with NaBH4. All of the catalysts could catalyze 4-NP to 4-AP, the results displayed the N-CoSe@C-800-4 possessed the highest catalytic activity which could totally convert 4-NP to 4-AP in only 40s reaction time at ambient temperature, which may be attributed to the N-CoSe@C-800-4 possessed high nitrogen content (4.15%). The morphology structure and composition of synthesized samples were characterized by SEM, TEM, EDX, XRD, XPS and Nitrogen adsorption/desorption measurements.

    更新日期:2018-01-10
  • Recent Progress in Ethylene Polymerization Catalyzed by Ni and Pd Catalysts
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-09
    Jun Wang, Li Wang, Haojie Yu, Raja Summe Ullah, Muhammad Haroon, Zain-ul Abdin, Xia Xia, Rizwan Ullah Khan

    Ethylene polymerization catalyzed by Ni and Pd catalysts is a highlight for academic research and industrial production. The structures of Ni and Pd catalysts can dramatically influence the performances of polymerization. In this review, the influence of newly reported Ni and Pd catalysts on the ethylene polymerization, from ligand effects to metal-metal cooperativity as well as the polymerization conditions, is discussed to provide fresh guidelines for rational design of the catalysts with high performances, highly efficient study of the polymerization mechanisms as well as successful synthesis of PE with unique microstructures and properties.

    更新日期:2018-01-10
  • "Zinc dihydride and mixed halo hydrides supported by an N-heterocyclic carbene"
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-09
    Arnab Rit, Ann-Kristin Wiegand, Debabrata Mukherjee, Thomas P. Spaniol, Jun Okuda

    A series of zinc dihalides [(IMes)ZnX2] [X = Cl (1a) Br (1b), I (1c); IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene] is reported. The iodide 1c undergoes salt metathesis with NaH as an alternative synthesis of [(IMes)ZnH2]2 (2). 2 readily reacted with (tBu)NCO and Ph2CO under ZnH insertion to give [(IMes)Zn(tBuNCHO-N)2] (3) and [(IMes)Zn(OCHPh2)2] (4), respectively. Ph2S2 and I2 oxidized the hydride ligands in 2 to give dihydrogen and [(IMes)Zn(SPh)2] (5) and 1c, respectively. A series of mixed halo hydrides [(IMes)Zn(X)(H)]2 [X = Cl (6a), Br (6b), I (6c)] was obtained upon comproportionating 2 with 1a-c. The new compounds were fully characterized including X-ray crystallographic analysis of 3 and 6b.

    更新日期:2018-01-10
  • Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-07
    Sara de Aguiar, Özgür Öztopcu, Anna Troiani, Giulia de Pdetris, Matthias Weil, Berthold Stöger, Ernst Pittenauer, Günter Allmaier, Luis Veiros, Karl Kirchner

    The synthesis of cationic mono oxo Mo(IV) PNP pincer complexes of the type [Mo(PNPMe-iPr)(O)X]+ (X = I, Br) from [Mo(PNPMe-iPr)(CO)X2] is described. These compounds are coordinatively unsaturated and feature a strong MoO triple bond. The formation of these complexes proceeds via cationic 14e intermediates [Mo(PNPMe-iPr)(CO)X]+ and requires both molecular oxygen and water. ESI MS measurements with 18O labeled water (H218O) and molecular oxygen (18O2) indicates that water plays a crucial role in the formation of the Mo≡O bond. A plausible mechanism based on DFT calculations is provided. The X-ray structure of [Mo(PNPMe-iPr)(O)I]SbF6 is presented.

    更新日期:2018-01-08
  • Bis(diethylamino)pentafluorophenylphosphane as valuable precursor for the design of novel tetrafluorophenylphosphanes, phosphinic and phosphonic acids
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-05
    Christian Alter, Beate Neumann, Hans-Georg Stammler, Berthold Hoge

    Facile replacement of the p-fluorine atom in bis-(diethylamino)pentafluorophenylphosphane [(Et2N)2PC6F5] by organolithium derivatives LiR (R = CH3, n-Bu, Ph), lithium alkoxides (R = OMe, OEt) and amides (NMe2, NEt2) is described. The obtained phosphanes p-R-C6F4-P(NEt2)2 are fully characterized. Their acid-catalysed hydrolysis affords the corresponding phosphinic acids p-R-C6F4-P(O)(H)OH, which are smoothly oxidized by treatment with a mixture of DMSO/I2 to phosphonic acids p-R-C6F4-P(O)(OH)2.

    更新日期:2018-01-05
  • Spontaneous Bicyclometalation of a Single Cobalt(I) Complex Stabilized via a δ-C-H Agostic Interaction
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-05
    Robert Beck, Sebnem Camadanli, Hans-Friedrich Klein

    CoCH₃(PMe₃)₄ is known for a long time for its potential to activate less reactive C-H Bonds under extremely mild conditions by methane elimination. A spontaneous second C-H bond activation at the same center of cobalt complex is not expected. In contrast to previous investigations with certain aryl-iminophosphane chelating ligands, in this work two consecutive metalation steps at the same complex center lead to a rare example of a cobalt metallabicycle. In the first step a C-H activation results in a five-membered chelate ring, whereas the second ring is formed by an incomplete C-H activation which stops at a stable, rarely observed δ-C-H agostic interaction. The results are supported by NMR spectroscopy, X ray structure analysis and density functional theory (dft) calculations. Knowledge of such agostic interactions are essential in order to understand catalytic reaction paths and studies of such molecular structures of their ring sizes, bite angles and electronic properties have shown that these ligands allow sensitive control within the metal coordination sphere.

    更新日期:2018-01-05
  • Impact of spin state transition on vibrations of [Fe-(PM-BiA)2 (NCS)2] and [Fe -(PM-PEA)2 (NCS)2] spin crossover compounds: experimental and theoretical far IR and Raman study.
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-04
    Amine Ould Hamouda, Benjamin Viquerat, Jérôme Degert, Samir Matar, Jean François Létard, François Guillaume, Eric Freysz

    Far IR and Raman spectroscopy of [Fe-(PM-BiA)2 (NCS)2] and [Fe -(PM-PEA)2 (NCS)2] are performed to record the vibration modes of these complexes and their evolutions during spin state transition. THz spectroscopy is used to measure the far IR absorption of these compounds down to 20 cm-1. Using density functional theory calculations we are able to retrieve and to visualize these vibrations in both high spin and low spin states. In both compounds, Raman spectra recorded in the 800 cm-1 2250 cm-1 wavenumber range are well accounted for by our computations. For far IR vibration modes, most of the experimental absorption peaks above 100 cm-1 are well reproduced. However, below 100 cm-1, marked difference are recorded. For [Fe-(PM-BiA)2 (NCS)2] we demonstrate that the interactions with surrounding molecules impacts non-negligibly the computed far IR spectra and can partly correct for this difference.

    更新日期:2018-01-04
  • N-Confused Porphyrin Metal Complexes with an Axial Pyridine Directly Tethered from an Inner Carbon: A Bioinspired Ligand as Versatile Platform for Catalysis
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-04
    Takaaki Miyazaki, Takaaki Yamamoto, Shunichi Mashita, Yuya Deguchi, Kazuki Fukuyama, Masatoshi Ishida, Shigeki Mori, Hiroyuki Furuta

    Bioinspired pentadentate ligand, N-confused porphyrin (NCP) bearing a 2-mercaptopyridine group (1), and its RuII and CoIII complexes, Ru(CO)-1a and Co(NO2)-1, were synthesized and the structures were revealed by single crystal X-ray analysis. Installation of an axial thiopyridine ligand negatively shifted the redox potentials and enhanced the catalytic activity largely, which was demonstrated in the cyclopropanation reaction using the Co complex.

    更新日期:2018-01-04
  • Nanoflakes-assembled 3D flower-like nickel oxide/nickel composite as supercapacitor electrode materials
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-04
    xue liu, fang liu

    Three-dimensional flower-like NiO/Ni composite was successfully prepared by a facile hydrothermal template-free method and followed by calcination in N2 atmosphere accompanied with glucose. The particles are assembled by porous nanoflakes. XRD, SEM, TEM, XPS measurements were performed to characterize the morphology and composition of the samples. The measurement results reveal that during the calcination process NiO was partially modified into Ni and consequently composite of NiO/Ni was obtained. Electrochemical tests of cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy were conducted in 6M KOH electrolyte solution. The test results show that the NiO/Ni composite exhibits a higher specific capacitance (363.7F/g at 0.5A/g) and better cycling stability than the as-prepared NiO. The preferable performances of the composite are attributed to the interconnected network of 3D structure, which provides more transport channels for electrolyte transportation and electrochemical active sites for faradaic reaction. The modified metal Ni forms conductive network on the surface and improves conductivity of the material, which favors for effective electrons transportation from surface to current collector. The results indicate the application potential of the NiO/Ni composite in electrode materials for supercapacitor.

    更新日期:2018-01-04
  • Synthesis of Phosphine-chalcogenides under Solvent-free Conditions using Rotary Ball Mill
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-03
    Rajnish Kumar, Saurabh Kumar, Madhusudan K Pandey, Vitthalrao S Kashid, Latchupatula Radhakrishna, Maravanji Shivaramaiah Balakrishna

    The mechanochemical technique of ball milling has been applied to the solvent-less and eco-friendly synthesis of chalcogenides (sulfide and selenide) of a variety of tertiary and amino-phosphines. In most of the cases, the products are obtained in almost quantitative yields with high purity by applying a simple workup procedure without using chromatographic techniques or any other purification methods. The scope of this methodology was explored by using a range of phosphines (mono, di and tetra) to synthesize partial as well as mixed-chalcogenides. The use of almost equimolar amounts of starting materials and absence of any by-product significantly simplifies the product isolation compared to the standard solution state reactions, thus providing a highly atom economic (100%) method with an ideal E-factor (E = 0). The solid state reactions were monitored by 31P{1H} NMR spectroscopy. The structures of some of the products are also confirmed by single crystal X-ray analyses. Although most of the reactions were carried out in ~100 mg scale, the scaling up of the reaction did not affect the course of the reaction.

    更新日期:2018-01-04
  • SnO2-based catalysts with low temperature performance for oxidative coupling of methane: insight into the promotional effects of alkali metal oxides
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-03
    Liang Peng, Junwei Xu, Xiuzhong Fang, Wenming Liu, Xianglan Xu, Liang Liu, Zhongchen Li, Renyang Zheng, Xiang Wang

    To develop reactive catalysts for oxidative coupling of methane at low temperature, different alkali metal oxides have been adopted to modify the surface of SnO2 in this study. In comparison with the un-modified SnO2, the reaction performance of all the modified catalyst can be significantly improved, among which lithium oxide shows the best promotional effects, and the optimal catalyst was achieved with a Sn/Li molar ratio of 5/5. Over this catalyst, the highest C2 product yield of 15.3 % has been achieved at 750 ℃. XPS and CO2-TPD results have revealed that for those catalysts with evident enhanced OCM reaction performance, the co-existence of suitable amount of surface alkaline and electrophilic oxygen sites is indispensable. Furthermore, over the catalysts modified by different amount of lithium oxide, the C2 yield at different temperatures is nearly proportional to the amounts of both surface intermediate alkaline sites and electrophilic oxygen species. Therefore, it is concluded that the abundance and the concerted interaction of these two types of surface active sites are the major factors determining the reaction performance of the SnO2-based catalysts. Last but not the least, the optimized catalyst, which has a Sn/Li molar ratio of 5/5 and also contains equal amounts of SnO2 and Li2SnO3 crystalline phases, exhibits much better reaction performance than Mn/Na2WO4/SiO2, the most promising catalyst at present, at low temperature region (below 750 ℃).

    更新日期:2018-01-03
  • Let the Celebrations Continue!
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2018-01-02
    Preeti Vashi
    更新日期:2018-01-02
  • Ruthenium p-cymene iminophosphonamide complexes: activation under basic conditions and transfer hydrogenation catalysis
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-29
    Iana S. Sinopalnikova, Tatyana A. Peganova, Natalia V. Belkova, Eric Deydier, Jean-Claude Daran, Elena S. Shubina, Alexander M. Kalsin, Rinaldo Poli

    Complex [(η6-Cym)RuCl(NPN)] {Cym = p-cymene; NPN = (p-TolN)2PPh2} (1) yields a thermally sensitive hydride derivative [(η6-Cym)RuH(NPN)] (2) by reaction with iPrOH in the presence of a strong base, via an observable isopropoxide intermediate [(η6-Cym)Ru(OiPr)(NPN)] (3), or with NaBHEt3 in THF. Partial conversion also occurs in iPrOH in the absence of base. 2 is stabilized by dihydrogen bonding with isopropanol, but attempts to isolate it induce isomerization by hydride migration to a ring CH position to yield [{η5-p-C6H5(Me)(iPr)}Ru(NPN)], which has been crystallographically characterized as a disordered mixture of two regioisomers (4/4'). 2 is an active catalyst for the transfer hydrogenation of acetophenone to phenylethanol in isopropanol. The catalytic transformation is first order in acetophenone and first order in catalyst, with k = 117±10 M-1 h-1 at 40°C. The temperature dependence of the rate constant (25-80°C) gave the activation parameters ΔH‡ = 9.6±1.3 kcal mol-1 and ΔS‡ = -31±4 cal mol-1 K-1. DFT calculations have validated the slow isomerization of 2 to 4/4' (high energy TS), the preference of the cyclohexadienyl system for 4/4' relative to the other isomers 4Me and 4iPr, where the hydride has migrated to the CMe or CiPr position, and suggest that the hydrogen transfer mechanism involves outer sphere hydride transfer to the ketone substrate with H-bonding assistance of isopropanol to yield a σ-complex intermediate [(η6-Cym)Ru+(NPN){H-C(Me)(Ph)O-}]

    更新日期:2017-12-31
  • Cover Feature: Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects (Eur. J. Inorg. Chem. /2018)
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-29
    Nisha Mammen, Leonardo Spanu, Eric C. Tyo, Bing Yang, Avik Halder, Sönke Seifert, Michael J. Pellin, Stefan Vajda, Shobhana Narasimhan
    更新日期:2017-12-31
  • Ethynyl Complexes of Gold(I) Formed by Transmetallation Using Tin(IV) or Silicon(IV) Compounds
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-29
    Karsten Klauke, Svenja Werner, Fabian Mohr
    更新日期:2017-12-31
  • Syntheses of the stable salts containing the hydridophosphate anion [P(C2F5)3F2H]-
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-28
    Julia Bader, Nikolai Ignat’ev, Berthold Hoge

    The reaction of the industrial product (C2F5)3PF2 with LiAlH4 in THF solution selectively furnished the hydridophosphate anion [P(C2F5)3F2H]-. The compound [PPh4][P(C2F5)3F2H] is obtained as a colourless solid on a multigram scale by salt metathesis in aqueous THF. Combining [P(C2F5)3F2H]- with various imidazolium and pyridinium cations affords ionic liquids with melting points well below room temperature. (C2F5)3PF2 also abstracts hydrides from amines, affording the hydridophosphate anion [P(C2F5)3F2H]- and the corresponding imminium cations which add a second amine moiety by intra- or intermolecular adduct formation.

    更新日期:2017-12-29
  • Structural and Thermal Properties of Air-Stable [Mg(1-methylimidazole)6][N(SO2CF3)2]2
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-29
    Yushen Wang, Gleb Veryasov, Kazuhiko Matsumoto, Rika Hagiwara
    更新日期:2017-12-29
  • Emergence of Surface- and Interface-Induced Novel Structures and Properties in Metal-Organic Framework Thin Films
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-27
    Tomoyuki Haraguchi, Kazuya Otsubo, Hiroshi Kitagawa

    Metal-organic frameworks (MOFs) are of particular interest to researchers because of their structural diversity and variety of properties. MOF thin films have been intensively investigated for potential applications such as membranes, gas sensors, catalysts, etc. Although most MOF thin films have almost the same structure and properties as their bulk, some MOF thin films show remarkable structural changes and hidden properties that are not observed in the bulk. These phenomena would be induced by the surface and the interface. Recent improvements in thin-film fabrication methods enabled us to construct MOF thin films and discuss the properties based on the structure, thickness and crystalline orientation in detail. This microreview describes and discusses the fascinating nature of MOF thin films originating from surface/interface. This paper is expected to help with the construction of a research strategy for MOF thin films to obtain hidden structures and properties of MOFs that are not observed in their bulk.

    更新日期:2017-12-28
  • Reminiscences of a Retiring Editor-in-Chief
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-27
    Karen Hindson
    更新日期:2017-12-27
  • Effect of temperature and pH on phase transformations in citric acid-mediated hydrothermal growth of tungsten oxide
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-25
    Kasper Wenderich, Johannes Noack, Anne Kärgel, Annette Trunschke, Guido Mul

    The temperature dependent composition of suspension during citric acid-mediated crystallization of tungsten trioxide (WO₃) from sodium tungstate was studied by in situ Raman spectroscopy. Additionally, microwave-assisted hydrothermal synthesis experiments combined with ex situ analysis by X-Ray diffraction and Scanning Electron Microscopy were performed to analyze the effect of pH on the eventually, isothermally, obtained crystal phase and morphology. The Raman results suggest that WO₃ · 2H₂O precipitates from the tungstate solution upon acidification to pH 0.5 at room temperature. This is first transformed to WO₃ · H₂O initiating at T = 70 °C. At temperatures above 170 °C, the crystallization of phase-pure monoclinic WO₃ with well-defined plate-like morphology was observed at pH 0.5. Using the microwave-assisted hydrothermal synthesis procedure shows that increasing the pH to values of 1.5 or 2 results in significant or dominant formation of hexagonal WO₃, respectively. Comparing the activity of selected samples in photocatalytic oxidation of propane using visible light, demonstrates the presence of hydrate phases or hexagonal WO₃ is detrimental to performance.

    更新日期:2017-12-27
  • An Esculetin-Cobalt(III) Archetype for Redox-Activated Drug Delivery Platforms with Hypoxic Selectivity
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-24
    Renata Crispim Batista, Carlos Basilio Pinheiro, Fabio da Silva Miranda, Mauricio Lanznaster

    The motivation of this work was to probe if coordination of esculetin to cobalt(III) could lead to a complex with the required properties to function as a redox-activated drug delivery platform, selective for hypoxic environments. The complex [Co(esc)(py2en)]ClO4.(CH3OH)2 (1) was obtained and fully characterized by CHN elemental analysis, single crystal X-ray diffractometry, UV-visible and fluorescence spectroscopies and ESI mass spectrometry. The redox behavior of 1 was evaluated by cyclic and square wave voltammetric analyses in MeCN and PBS buffer, which revealed distinct potentials for the Co3+/Co2+ processes in aqueous and organic solutions. In PBS, the potential fell within the accepted ideal range (-0.2 to -0.4 V vs SHE) for reduction in biological systems. Thus, a selective release of the coumarin ligand, under hypoxic environment upon reduction, was simulated by investigating reactions of 1 with sodium dithionite under argon, air and O2-saturated atmospheres. An [O2]-dependent dissociation of esculetin was observed over a 72 h period at 25 oC by UV-visible monitoring, and confirmed by fluorescence spectroscopy and ESI-MS data. These results provided strong evidence of a hypoxia-selective, redox-activated mechanism for the release of esculetin from the cobalt(III) complex.

    更新日期:2017-12-27
  • The [Fe[(SePPh2)2N]2] complex revisited: X-ray crystallography, magnetometry, high-frequency EPR and Mössbauer studies reveal its tetrahedral FeIISe4 coordination sphere
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-22
    Eleftherios Ferentinos, Spyros Chatziefthimiou, Athanassios Boudalis, Michael Pissas, Guinevere Mathies, Peter Gast, Edgar Groenen, Yiannis Sanakis, Panayotis Kyritsis

    The synthesis and characterization of a preparation of the [Fe{(SePPh2)2N}2] complex (1) is described. X-ray crystallography shows that this system contains a tetrahedral FeSe4 coordination sphere. The structural features of 1 are compared with those of similar first row transition element complexes, including a recently reported preparation of [Fe{(SePPh2)2N}2] (1SP) exhibiting a highly unusual square planar FeSe4coordination sphere. The electronic structure of 1 was elucidated by magnetometry, high-frequency EPR, and Mössbauer spectroscopic studies, which reveal zero-field splitting (ZFS) parameters typical of high spin S = 2 tetrahedral FeII sites. Accurate ZFS parameters (D = +8.22 cm−1, E/D = 0.104) were obtained by analysis of the EPR spectra and compared with those of the analogous [Fe{(SPPh2)2N}2] complex.

    更新日期:2017-12-22
  • Uranyl Ion Complexes with Chiral Malic and Citramalic, and Prochiral Citric and Tricarballylic Acids: Influence of Coligands and Additional Metal Cations
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-21
    Pierre Thuery, Jack Harrowfield

    Seven homo- or heterometallic uranyl ion complexes with R,S-malic (H3ml), R-citramalic (H3cml), citric (H4cit) and tricarballylic (H3tca) acids were obtained under (solvo-)hydrothermal conditions and characterized by their crystal structure and, for five of them, their uranyl emission spectrum. All the malate, citramalate and citrate complexes contain the frequently observed 2:2 dimeric uranyl subunit in which the alkoxide group is bridging, these subunits being generally assembled into one-dimensional (1D) polymeric chains by bridging carboxylate groups. [(UO2)4(ml)2(C2O4)(NMP)4] (1) and [(UO2)2Cu2(ml)2(C2O4)(phen)2] (2), which contain oxalate anions formed in situ, crystallize as two-dimensional (2D) networks, the increase in dimensionality being provided by uranyl or copper oxalate bridges. [(UO2)2Ni(cml)2(cyclam)] (3) is also a 2D species, while [(UO2)2Cd(cml)2(bipy)(H2O)2] (4) crystallizes as a three-dimensional (3D) framework (even if CdII cations are disregarded). [(UO2)2Zn(Hcit)2(bipy)2(H2O)] (5) is a 1D polymer with decorating Zn(bipy)2(H2O)2+ groups, while [(UO2)2Cd(Hcit)2(bipy)2] (6) is a 2D network. [(UO2)2Pb(tca)2(H2O)4] (7), in which the three carboxylate groups are chelating and two of them further bridging, is a 3D framework. The uranyl emission spectra of complexes 3-6 are in agreement with a previously described trend, the largest blue-shift being found for the eight-coordinate complex 7.

    更新日期:2017-12-22
  • Photolabile [Ru([9]aneS3)(chel)(py)][Cl]2 (chel = chelating diimine) model complexes for light-triggered drug release
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-21
    Federica Battistin, Gabriele Balducci, Jianhua Wei, Anna Renfrew, Enzo Alessio

    A series of water-soluble photolabile model complexes of the general formula [Ru([9]aneS3)(chel)(py)][Cl]2 ([9]aneS3 = 1,4,7-trithiacyclononane, chel = chelating diimine) was prepared and fully characterized. The photo-triggered release of pyridine with visible light as a function of the nature of the diimine (chel = 2,2′-bipyridine (6) 1,10-phenanthroline (7), 4,7-diphenil-1,10-phenanthroline (8), dipyrido-[3,2-a:2′,3′-c]phenazine (dppz, 9), 2,2′-biquinoline (bq, 10)) was investigated. Our aim is that of establishing if this type of complexes in the future might be realistically used in the photo-uncaging strategy of photoactivated chemotherapy (PACT). When irradiated with light at 470 nm, they rapidly and quantitatively release the coordinated pyridine. Complex 10 turned out to be quite different from to the others in the series. Structure-wise, in 10 the average plane of coordinated bq is remarkably tilted relative to the equatorial coordination plane (37.43 (4)°) and the orientation of py is ca. orthogonal compared to that found in 6 and 7. The low-lying acceptor orbitals of bq induce a red-shift of the MLCT absorption maximum to ca. 500 nm. Contrary to the expectations, complex 10 is more photo-stable compared to 6 - 9 and photo-dissociation of both py and bq, in ca. equal amounts, occurs. A detailed theoretical investigation was performed on 10 (and on 6 for comparison), for explaining its peculiar spectral features and photochemical behavior.

    更新日期:2017-12-21
  • Magnetism in heterobi- and hetrotrimetallic chains based on the use of [WV(bipy)(CN)6]- as a metalloligand
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-21
    Marius Andruh, Maria-Gabriela Alexandru, Diana Visinescu, Sergiu Shova, Miguel Julve, Francesc Lloret

    Two new heterobi- and trimetallic chains of formula ∞1[{MnII(pyim)2}{(µ-NC)2WV(bipy)(CN)4}][WV(bipy)(CN)6] (1) and ∞1[{CuIIMnIIL}{(µ-NC)3WV(bipy)(CN)3}][WV(bipy)(CN)6]·0.75H2O·2MeCN (2) were obtained by reacting the cyanido-based AsPh4[W(bipy)(CN)6] heteroleptic complex with the pre-formed [MnII(pyim)2]2+ (1) and [CuIIMnIIL]2+ (2) complexes [bipy = 2,2'-bipyridine, pyim = 2-(1H-imidazol-2-yl)pyridine and H2L = macrocyclic Schiff-base resulting from the stepwise condensation of 2,6-diformyl-p-cresol with ethylenediamine and diethylenetriamine]. The structure of 1 consists of cationic cyanido-bridged {MnIIWV} chains, assembled from [WV(bipy)(CN)6]- spacers, each one coordinating in a bis-monodentate fashion, two [MnII(pyim)2]2+ nodes, and [WV(bipy)(CN)6]- counteranions. Compound 2 comprises a positively charged 1D coordination polymer, built from [WV(bipy)(CN)6]- cyanido metalloligands that act as tris-monodentate spacers towards [CuIIMnIIL]2+ complexes, the entire assembly being neutralized by [WV(bipy)(CN)6]- anions. The magnetic susceptibility of 1 and 2 investigated down to 1.9 K is characteristic of 1D ferrimagnetic behavior with minima in the MT versus T plots at 35 (1) and 20 K (2).

    更新日期:2017-12-21
  • Ammonothermal Synthesis and Crystal Structure of the Nitridoalumogermanate Ca1-xLixAl1-xGe1+xN3 (x ≈ 0.2)
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-21
    Jonas Häusler, Lucien Eisenburger, Oliver Oeckler, Wolfgang Schnick

    The new nitridoalumogermanate Ca1-xLixAl1-xGe1+xN3 (x ≈ 0.2) was synthesized from supercritical ammonia at 925 K and 185 MPa starting from the intermetallic precursor Ca3Al2Ge2 and Li as mineralizer. The crystal structure was refined by the Rietveld method; Ca1-xLixAl1-xGe1+xN3 with x ≈ 0.2 (a = 9.9822(5), b = 5.7763(2), c = 5.1484(1) Å, Z = 4, Rwp = 0.0492) crystallizes in orthorhombic space group Cmc21 (no. 36). Needle-shaped crystals with up to 15 µm in length were detected by scanning electron microscopy. Possible cation ordering was analyzed by transmission electron microscopy. No superstructure reflections were observed in electron diffraction patterns and the structure model was confirmed by Z-contrast imaging. The composition was verified by energy-dispersive X-ray spectroscopy on single crystals and inductively coupled plasma optical emission spectrometry. Optical properties were studied by diffuse reflectance spectroscopy, showing a broad absorption band between 250 and 300 nm. The optical band gap was estimated to be 4.3 eV at room temperature using the Tauc method.

    更新日期:2017-12-21
  • Reagent regulated oxidative O-demethylation of a ferrous complex stabilized by tetradentate N-ligand having a methoxyphenyl substituent
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-21
    Anjana S S, Babu Varghese, Prasad Edamana

    A ferrous complex FeLOMeCl2, 1 where LOMe is 2-methoxy-N,N-bis(pyridin-2-ylmethyl) aniline, has been synthesized and its structural, spectral and reactivity studies have been carried out. The complex has rich spectral properties and shows a well-defined paramagnetic 1H NMR spectrum with sharp and hyperfine shifted signals, which were assigned with the help of a combination of 1H-1H COSY and T1 and T2 relaxation time measurements. Though stable to air, 1 underwent oxidation in presence of AgClO4, resulting in the formation of a symmetric diferric oxo complex [(LOMeFeIIICl)2O](ClO4)2, 2. However, on reaction with strong oxidants like t-BuOOH, 1 yielded a mixture of an unsymmetric diferric oxo complex LOMeFeIIIClOFeIIICl3, 3 and a mononuclear ferric complex LO-FeIIICl2, 4 with modified phenoxide ligand LO-, which is formed as a result of the demethylation of LOMe during oxidation. The factors affecting O-demethylation were studied and a possible mechanistic pathway involving a high valent iron-oxo species is proposed.

    更新日期:2017-12-21
  • Bond Analysis in Dihalogen…Halide and Dihalogen…Dimethylchalcogenide Systems
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-20
    Felipe Scheinder, Giovanni Finoto Caramori, Renato Parreira, Vito Lippolis, Massimiliano Arca, Gianluca Ciancaleoni

    The bonding in mixed chalcogen/halogen three-body systems of general formula XI…Y (X = Cl, Br, I; Y = I-, EMe2; E = S, Se, Te) has been theoretically examined by using different methodologies, namely Charge Displacement (CD) analysis, which quantifies the electronic flux throughout the whole adduct, Energy Decomposition Analysis-Natural Orbital for Chemical Valence (EDA-NOCV) and zeroth order Symmetry Adapted Perturbation Theory (SAPT0), both of which decompose the contributions of the interaction energy between XI and Y into physical meaningful terms. It is known that in the solid state the distribution of the relative elongations of the two bonds (δXI and δIY) in the three-body systems examined here can be rationalized in terms of only one common equation derived from the bond-valence model. According to CD and EDA-NOCV, the charge transfer between the two fragments does not depend on the exact nature of the atoms involved, but only on the values of δXI and δIY, with variability of 0.05 e and on the total charge of the system. On the other hand, using the SAPT0 method and computing the polarization-free value of the charge transfer between the two fragments, it results to be the same for all the systems with the same δXI and δIY, irrespectively not only of the nature of the atoms, but also of the total charge of the system (anionic and neutral).

    更新日期:2017-12-21
  • Sphalerite Cu/ZnS nanoparticles derived from Cu/Zn-ZIF-8 for photocatalytic degradation and adsorption of dyes
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-19
    Gang Xiong, Yanan wang, Yaguang Sun, Lixin You, Baoyi Ren, Zhenhe Xu, Yongke He, Laurent Ruhlmann, Fu Ding

    A series of Cu-doped ZnS sphalerite nanoparticles have been synthesized by mean of the reaction between the Cu2+-doped zeolitic imidazolate frameworks (ZIF-8) with different Cu:Zn molar ratio moles as metal sources and different sulfur sources such as carbon disulfide (CD), thioacetamide (TAA), sodium sulfide (SS) and thiourea (TU) under solvothermal condition. The Cu-doped ZnS samples almost exhibited nano - sphere morphologies with less than 100 nm diameters and high BET surfaces. Photocatalytic properties of the obtained samples are investigated for the photodegradation of methylene blue (MB) aqueous solution as representative under visible light illumination. The results indicated that Cu/ZnS-20-SS presented a remarkable photocatalytic degradation rate of more than 90% during 1 hour and re-usability four times without major loss of activities. In additional, adsorption investigation revealed that the series of Cu/ZnS-TAA can rapidly adsorb dyes such as MB and Methyl orange (MO) with high adsorption capacities of about 260 mg/g within 10 minutes, and saturated adsorption capacities of nearing to 300 mg/g can be achieved.

    更新日期:2017-12-20
  • The influence of acids on tuning the pore size of mesoporous TiO2 templated by non-ionic block copolymers
    Eur. J. Inorg. Chem. (IF 2.444) Pub Date : 2017-12-19
    Stefano Loreto, Hans Vanrompay, Myrjam Mertens, Sara Bals, Vera Meynen

    We show the possibility to tune the pore size of mesoporous TiO2 templated by non-ionic block copolymers by adding different inorganic acids at well-chosen concentration. The effect of the inorganic anions on both the TiO2 cluster formation and the non-ionic block copolymers micelles is investigated to explain the experimental results

    更新日期:2017-12-19
  • 更新日期:2017-12-19
Some contents have been Reproduced with permission of the American Chemical Society.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
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