European Journal of Inorganic Chemistry

Cover image for Vol. 2014 Issue 12

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

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 3.12

ISI Journal Citation Reports © Ranking: 2012: 11/44 (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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  3. 41 - 52
  1. Full Papers

    1. Hexacoordinate Silicon

      Neutral Hexacoordinate Silicon(IV) Complexes with a Tridentate Dianionic O,N,X Ligand (X = O, N, S), Bidentate Monoanionic X,N Ligand (X = O, S), and Phenyl Ligand: Compounds with a SiO3N2C, SiSO2N2C, SiO2N3C, SiSON3C, or SiS2ON2C Skeleton

      Jörg Weiß, Johannes A. Baus, Christian Burschka and Reinhold Tacke

      Article first published online: 3 APR 2014 | DOI: 10.1002/ejic.201400083

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      A series of neutral hexacoordinate silicon(IV) complexes have been synthesized and structurally characterized by NMR spectroscopy and single-crystal X-ray diffraction. These studies were performed with a special emphasis on comparing the respective O/NMe/S analogues 4a/5a/6a and 4b/5b/6b and the O/S pairs 4a/4b, 5a/5b, and 6a/6b with respect to their structures and NMR spectroscopic parameters.

    2. Metal–Organic Frameworks

      Construction of Metal–Organic Frameworks Consisting of Dinuclear Metal Units Based on 5-Hydroxyisophthalate and Flexible Dipyridyl Ligands

      Xiaoju Li, Tena Guan, Xiaofang Guo, Xinxiong Li and Zhenjiang Yu

      Article first published online: 3 APR 2014 | DOI: 10.1002/ejic.201400092

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      Four CoII and CuII metal–organic frameworks consisting of dinuclear metal units have been constructed from rigid 5-hydroxyisophthalate (ip-OH) and flexible dipyridyl ligands. The ip-OH bridging modes and the metal coordination geometries are very different in the four complexes. Magnetic studies indicate the existence of antiferromagnetic exchange between the metal centers.

  2. Short Communications

    1. A Luminescent Metallacycle

      A Luminescent Rhenium(I) Metallacycle with Oxygen and Nitrogen Donor Atoms: Photophysical and Theoretical Studies

      Dibyendu Bhattacharya

      Article first published online: 3 APR 2014 | DOI: 10.1002/ejic.201400067

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      A new N,O-bischelator-bridged D-type self-assembled ReI metallacycle exhibits unusual multiple emission with moderate luminescence (Φem = 0.26, average radiative decay lifetime, τr = 0.052 μs). An improvement of the luminescence efficiency on traversing from ReC3N3 to ReC3N2O to ReC4N2 has been established based on photophysical and DFT results.

  3. Full Papers

    1. Iridium Complexes

      Intramolecular π Stacking in Cationic Iridium(III) Complexes with Phenyl-Functionalized Cyclometalated Ligands: Synthesis, Structure, Photophysical Properties, and Theoretical Studies

      Peng Li, Guo-Gang Shan, Hong-Tao Cao, Dong-Xia Zhu, Zhong-Min Su, Rukkiat Jitchati and Martin R. Bryce

      Article first published online: 3 APR 2014 | DOI: 10.1002/ejic.201400007

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      A combined experimental and theoretical study of the cationic iridium complexes [Ir(dppy)2phen]PF6 (1) and [Ir(tppy)2phen]PF6 (2) is described. The complexes are green photoemitters. Strong intramolecular π–π stacking leads to enhanced distortions in the geometry of the complexes, which is detrimental to their use in light-emitting electrochemical cells (LECs).

    2. DNA Cleavage

      Synthesis, Crystal Structures, and DNA Cleavage Activities of Manganese(II) Complexes: A Good Example of the Synergy between Metal Ions Prompting DNA Cleavage

      Li-Na Zhu, Huan-Rui Gao, Hai-Xian Wang, Ming-Yuan Xu and Xiao-Zeng Li

      Article first published online: 3 APR 2014 | DOI: 10.1002/ejic.201400044

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      The higher DNA cleavage abilities of multinuclear MnII complexes than their mononuclear analogue and the highest DNA cleavage efficiency of the complex with the shortest Mn···Mn distance and the strongest magnetic coupling between the MnII ions confirm the great effect of the synergy between metal centers on DNA cleavage efficiencies.

    3. Self-Assembly

      Self-Assembled Cages from the Electroactive Bis(pyrrolo)tetrathiafulvalene (BPTTF) Building Block

      Sébastien Bivaud, Sébastien Goeb, Jean-Yves Balandier, Marcos Chas, Magali Allain and Marc Sallé

      Article first published online: 31 MAR 2014 | DOI: 10.1002/ejic.201400060

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      An expeditive synthesis of electroactive di- and tetratopic ligands based on bis(pyrrolo)tetrathiafulvalene (BPTTF) is described. The coordination-driven self-assembly of these ligands with cis-protected PtII complexes affords the first examples of 3D cages incorporating the electron-rich TTF unit. These ligands are also able to undergo an original conversion to heteroleptic dithiolene complexes.

  4. Microreviews

    1. Copper Peptides

      De Novo Designed Copper α-Helical Peptides: From Design to Function

      Matteo Tegoni

      Article first published online: 31 MAR 2014 | DOI: 10.1002/ejic.201400057

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      De novo designed α-helical peptides have been used to design structural and functional copper sites in minimum protein scaffolds. The design of structural copper Type 1, Type 2, Type A, and Cu–SCys centers in α-helical constructs is described. Catalytic copper Type 2 centers are also presented, along with their functional features.

  5. Short Communications

    1. Red Emitters

      Hexamolybdenum Cluster Complexes with Pyrene and Anthracene Carboxylates: Ultrabright Red Emitters with the Antenna Effect

      Kaplan Kirakci, Karla Fejfarová, Monika Kučeráková and Kamil Lang

      Article first published online: 27 MAR 2014 | DOI: 10.1002/ejic.201402076

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      An antenna system based on a hexamolybdenum cluster complex with strongly absorbing ligands displays unprecedented brightness of red emission upon excitation in the near-UV region.

  6. Full Papers

    1. Graphene–Porphyrin Structures

      Structures Self-Assembled from Anionic Graphene and Cationic Manganese Porphyrin: Characterization and Application in Artificial Photosynthesis

      Amir Kaplan, Eli Korin and Armand Bettelheim

      Article first published online: 27 MAR 2014 | DOI: 10.1002/ejic.201400054

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      Carboxylic-rich graphene oxide and MnIII tetrakis(N-methyl-4-pyridinio)porphyrin form self-assembled structures through π–π stacking interactions. When adsorbed on iron/hematite photoanodes, these structures show substantial activity towards the photoelectrochemical oxidation of water.

    2. Waste Prevention

      Sodium “Activation” of Silano-Phosphonate Modified Mesoporous TiO2 Leading to Improved Rare-Earth Element Extraction

      Mícheál P. Moloney, Jérémy Causse, Cedric Loubat and Agnès Grandjean

      Article first published online: 27 MAR 2014 | DOI: 10.1002/ejic.201400027

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      Mesoporous silano-phosphate functionalised TiO2 particles are used to separate Ce3+ from Sr2+ and Cs+, as well as other rare earths. Unlike SiO2, the resistance of TiO2 to strong base allowed for the phosphonate to be activated by a base, increasing its sorption ability threefold.

    3. Catalytic Hydrolysis

      A Heterobimetallic FeIIIMnII Complex of an Unsymmetrical Dinucleating Ligand: A Structural and Functional Model Complex for the Active Site of Purple Acid Phos­phatase of Sweet Potato

      Biswanath Das, Henrik Daver, Amrendra Singh, Reena Singh, Matti Haukka, Serhiy Demeshko, Franc Meyer, George Lisensky, Martin Jarenmark, Fahmi Himo and Ebbe Nordlander

      Article first published online: 26 MAR 2014 | DOI: 10.1002/ejic.201301375

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      Catalytic hydrolysis of a phosphodiester bond was investigated by using a mixed-valence heterodinuclear FeIIIMnII complex of the dinucleating ligand as catalyst. Computational modeling and kinetic results indicate that a μ-hydroxo FeIIIMnII complex is the active catalyst that binds the substrate in a monodentate fashion at the Mn ion.

  7. Short Communications

    1. Tungstophosphoric Acid Catalysts

      Synthesis and Characterization of Tungstophosphoric Acid/Pentaethylenehexamine/ZrSBA-15 and Its Use in the Selective Oxidation of Benzyl Alcohol under Solvent-Free Conditions

      Ling-Yan Meng, Shang-Ru Zhai, Shi Li, Bin Zhai, Qing-Da An and Xiao-Wei Song

      Article first published online: 25 MAR 2014 | DOI: 10.1002/ejic.201402028

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      A layer-by-layer deposition strategy was used for the preparation of a tungstophosphoric acid/pentaethylenehexamine/ZrSBA-15 composite. This recyclable material was stable at high temperatures and in polar solvents, and it exhibited excellent catalytic properties (84.7 % conversion, >99 % selectivity) in the selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (BzH).

  8. Full Papers

    1. Oxidovanadium Complexes

      Mitochondria-Targeted Photoinduced Anticancer Activity of Oxidovanadium(IV) Complexes of Curcumin in Visible Light

      Puja Prasad, Ila Pant, Imran Khan, Paturu Kondaiah and Akhil R. Chakravarty

      Article first published online: 25 MAR 2014 | DOI: 10.1002/ejic.201402001

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      A Schiff-base oxidovanadium(IV) complex of curcumin bearing a pendant naphthalimide specifically targets cellular mitochondria and exhibits remarkable photocytotoxicity in visible light with low dark toxicity in keratinocyte HaCaT and breast cancer MCF-7 cells. The apoptotic cell death involves 1O2 and ·OH species.

    2. Luminescent Coordination Polymers

      Nitrile-Supported Coordination Polymers of Cerium(III) Bromide

      Kalyan V. Vasudevan, William L. Boncher, Nickolaus A. Smith, Michael W. Blair, Brian L. Scott, Bryan L. Bennett, Markus P. Hehlen, Ross E. Muenchausen and John C. Gordon

      Article first published online: 25 MAR 2014 | DOI: 10.1002/ejic.201400030

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      Cerium bromide coordination polymers have been prepared and structurally authenticated on the basis of X-ray diffraction data. The photoluminescence spectra of the polymers feature considerably redshifted emission bands compared to the characteristic emission observed for CeBr3 single crystals.

    3. Luminescence

      Photophysical Properties of a Series of Rhenium Selenide Cluster Complexes Containing Nitrogen-Donor Ligands

      Wade B. Wilson, Kevin Stark, Dean B. Johnson, YiXin Ren, Hitoshi Ishida, David L. Cedeño and Lisa F. Szczepura

      Article first published online: 25 MAR 2014 | DOI: 10.1002/ejic.201301626

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      The photophysical properties of thirteen [Re6Se8]2+ clusters containing N-donor ligands are reported. The impact of para substituents on luminescence was investigated by using a series of benzonitrile and phenyl-substituted tetrazolate complexes. CV and DFT studies support metal-to-ligand charge transfer (MLCT) character in the excited-state wave function for the p-nitrobenzonitrile complex.

    4. Oxide Semiconductors

      Dimethylmalonato Zinc Complexes as Molecular Precursors for Electronic Grade Zinc Oxide: Towards a Systematic Ligand Design by Understanding Molecular Decomposition Mechanisms

      Rudolf C. Hoffmann and Jörg J. Schneider

      Article first published online: 25 MAR 2014 | DOI: 10.1002/ejic.201301525

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      Zn complexes with malonato ligands functionalized in the 2-position are suitable precursors for solution processed ZnO. A detailed investigation of the decomposition mechanism shows the influence of nitro and hydroxylimino groups on the ceramisation process. The precursors allow the formation of nanocrystalline ZnO which can be used as semiconductor material in field-effect transistors.

    5. Ring-Opening Polymerization

      Synthesis, Structure, and Catalytic Activity of Tridentate, Base-Functionalized β-Ketiminate Zinc Complexes in Ring-Opening Polymerization of Lactide

      Christoph Scheiper, Dennis Dittrich, Christoph Wölper, Dieter Bläser, Joachim Roll and Stephan Schulz

      Article first published online: 25 MAR 2014 | DOI: 10.1002/ejic.201301462

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      Several NNO zinc complexes were synthesized and structurally characterized by single-crystal X-ray diffraction. In addition, their catalytic activity in the ring-opening polymerization (ROP) of lactide is presented. The polymerization occurs through a modified activated-monomer mechanism.

    6. Lanthanides

      Magnetic Studies of Redox-Active Tetrathiafulvalene-Based Complexes: Dysprosium vs. Ytterbium Analogues

      Julie Jung, Tamyris T. da Cunha, Boris Le Guennic, Fabrice Pointillart, Cynthia L. M. Pereira, Javier Luzon, Stéphane Golhen, Olivier Cador, Olivier Maury and Lahcène Ouahab

      Article first published online: 21 MAR 2014 | DOI: 10.1002/ejic.201400121

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      The crystal-field energy splitting of the ground-state multiplets of the complexes Dy and Yb was evaluated, and they demonstrate Ising and non-Ising character. Both anisotropy axis directions for the MJ ground states were determined in agreement with the oblate and prolate electronic distribution for DyIII and YbIII ions. This results in SMM and non-SMM behaviour for Dy and Yb, respectively.

    7. Cucurbituril Supramolecular Arrays

      Cucurbituril-Based Supramolecular Self-Assemblies Formed in the Presence of Alkali Metal and Cadmium Ions

      Hang Cong, Yi Zhao, Li-Li Liang, Kai Chen, Xiao-Jie Chen, Xin Xiao, Yun-Qian Zhang, Qian-Jiang Zhu, Sai-Feng Xue and Zhu Tao

      Article first published online: 21 MAR 2014 | DOI: 10.1002/ejic.201400004

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      We describe herein three new cucurbituril-based coordination supramolecular arrays self-assembled in the presence of alkali metal and cadmium ions.

    8. Lanthanide Complexes

      Lanthanide Complexes with Tetradentate N,N′,O,O′-Dipyridyl-Based Ligands: Structure, Stability, and Photophysical Properties

      Nataliya E. Borisova, Andrey A. Kostin, Elizaveta A. Eroshkina, Marina D. Reshetova, Konstantin A. Lyssenko, Evgenia N. Spodine and Lada N. Puntus

      Article first published online: 21 MAR 2014 | DOI: 10.1002/ejic.201301271

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      Complexes of LnIII with N,N′,O,O′-tetradentate dipyridyl-based ligands were synthesized. Their structures were studied by X-ray diffraction, and their binding constants were determined by UV/Vis titration. Structure–property relationships were partly revealed by DFT calculations of the potential energy surface (PES) for three ligands, which show different efficiencies in extracting AmIII.


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