European Journal of Inorganic Chemistry

Cover image for Vol. 2017 Issue 43

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

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.444

ISI Journal Citation Reports © Ranking: 2016: 13/46 (Chemistry Inorganic & Nuclear)

Online ISSN: 1099-0682

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

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  1. Full Papers

    1. Temperature Sensors

      Structure- and Temperature-Dependent Luminescence Properties of Threefold Interpenetrated Networks: Coordination Polymers Based on Dinuclear Gridlike Silver(I) Units

      Shun-Ze Zhan, Huan-Quan Song, Liu-Jun Guo, Raymond Wai-Yin Sun and Dan Li

      Version of Record online: 26 SEP 2017 | DOI: 10.1002/ejic.201700662

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      Dinuclear AgI structural units with (3-pyridyl)-5-R-pyrazole ligands are extended from oligomers (R = phenyl) to threefold interpenetrated 3D coordination polymers (R = 3-pyridyl) with cds-a (augmented CdSO4) nets linked through supramolecular interactions (Ag–ligand, Ag–anion, Ag–Ag, and π–π). They show temperature-dependent luminescence and are candidates for luminescence thermometers.

    2. Phosphaguanidines

      Basicity of N-(Tetramesityltetraphosphacyclopentylidene)cyclohexylamine: An Unusual Diphospha(III)guanidine Derivative

      Anup Kumar Adhikari, Toni Grell, Peter Lönnecke and Evamarie Hey-Hawkins

      Version of Record online: 22 SEP 2017 | DOI: 10.1002/ejic.201700869

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      The nitrogen atom in cyclic hetero-oligophosphane cyclo-P4Mes4C(NCy) (1) can be protonated with HCl or HBF4. The resulting cation was isolated as the BF4, AlCl4 and GaCl4 salts. According to quantum mechanical calculations, the basicity of compound 1 is comparable to that of methyl-substituted monophospha(III)guanidine. The experimentally determined pKα value is in the range of 4.9–5.2.

  2. Microreviews

    1. Metallosalens

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      Introducing Metallosalens into Biological Studies: The Renaissance of Traditional Coordination Complexes

      Hao-Yan Yin, Juan Tang and Jun-Long Zhang

      Version of Record online: 19 SEP 2017 | DOI: 10.1002/ejic.201700695

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      Metallosalens are traditional metal complexes known since the 1930s and have recently found new applications in diverse biological fields including DNA binding, fluorescence imaging, and as MRI contrast agents and potential drugs.

  3. Full Papers

    1. Luminescence Quenching Mechanisms

      Modulation of the Photophysical Properties of 1-Azathioxanthones by Eu3+, Gd3+, Tb3+, and Yb3+ Ions in Methanol

      Riikka Arppe, Nicolaj Kofod, Anne Kathrine R. Junker, Lea G. Nielsen, Elena Dallerba and Thomas Just Sørensen

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/ejic.201700720

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      Strong lanthanide centered luminescence signals require efficient excited state energy transfer from antenna chromophore, but how do we design systems with rapid and efficient energy transfer?

    2. Chemosensors

      An Azacrown[N,S,O]–Styryl Modified Boron–Phenylpyrrin: Coordination-Mode-Transition-Induced Colorimetric and OFF–ON–OFF Fluorescence Chemosensor for Quantifying Cu2+

      Yuting Chen, Houhe Pan, Kang Wang, Dongdong Qi and Jianzhuang Jiang

      Version of Record online: 15 SEP 2017 | DOI: 10.1002/ejic.201700653

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      A new p-azacrown[N,S,O]–styryl modified boron–phenylpyrrin compound, possessing a diethylamino receptor, acts as a highly sensitive colorimetric and OFF–ON–OFF fluorescence sensor for quantifying Cu2+ associated with the sequential transition from free ligand (L) to 1:1 (ML) and 2:1 (M2L) complexes, due to the different Cu2+ complexing affinities of the p-azacrown[N,S,O] and diethylamino moieties.

    3. Luminescent Copper(I) Complexes

      Thermal and Mechanochemical Syntheses of Luminescent Mononuclear Copper(I) Complexes

      Panyi Liang, Atsushi Kobayashi, Tatsuya Hasegawa, Masaki Yoshida and Masako Kato

      Version of Record online: 15 SEP 2017 | DOI: 10.1002/ejic.201700734

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      Three mononuclear CuI iodide complexes with triphenylphosphine and isoquinoline derivatives were synthesized by conventional solution reactions, mechanochemical syntheses, and thermal syntheses. Complexes with amino-functionalized isoquinoline exhibited yellow or orange phosphorescence from the 3ππ* excited state, although those with nitro-functionalized isoquinoline did not show emission.

    4. Upconverting Phosphors

      Expanding the Scope of Biomolecule Monitoring with Ratiometric Signaling from Rare-Earth Upconverting Phosphors

      Chloë Oakland, Michael B. Andrews, Letitia Burgess, Alex Jones, Sam Hay, Peter Harvey and Louise S. Natrajan

      Version of Record online: 13 SEP 2017 | DOI: 10.1002/ejic.201700717

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      A one-pot synthesis of thulium and erbium lanthanide doped upconverting phosphors capped with three different functional groups ratiometrically sense the presence of cofactors in key biomolecules through energy transfer and report on enzyme activity of flavoproteins with substrates.

  4. Communications

    1. Doped Silica Nanoparticles | Very Important Paper

      Collective Properties Extend Resistance to Photobleaching of Highly Doped PluS NPs

      Damiano Genovese, Enrico Rampazzo, Nelsi Zaccheroni, Marco Montalti and Luca Prodi

      Version of Record online: 13 SEP 2017 | DOI: 10.1002/ejic.201700831

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      Highly dye-doped nanoparticles are shown to be long-lasting, super-photostable probes under strong excitation conditions. Self-quenched dyes act as intensity “buffers”, keeping the brightness constant for a long period of time. The observed phenomenon is a collective property arising from the fast communication between dyes and the resulting preferential photobleaching of self-quenched fluorophores.

  5. Full Papers

    1. Size Effects of Nanoparticles

      Elasticity of Prussian-Blue-Analogue Nanoparticles

      Gautier Félix, Mirko Mikolasek, Helena J. Shepherd, Jérôme Long, Joulia Larionova, Yannick Guari, Jean-Paul Itié, Aleksandr I. Chumakov, William Nicolazzi, Gábor Molnár and Azzedine Bousseksou

      Version of Record online: 11 SEP 2017 | DOI: 10.1002/ejic.201700796

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      The elastic behavior of Prussian-blue-analogue nanoparticles has been investigated, using high-pressure synchrotron X-ray diffraction and nuclear-inelastic-scattering techniques. We have extracted all of the elastic moduli for different sizes of Prussian-blue-analogue nanoparticles. This result is the basis for understanding electron–lattice coupling phase transitions at the nanoscale.

    2. Mixed-Valent Manganese Cages | Very Important Paper

      Evidence of Spin Canting, Metamagnetism, Negative Coercivity and Slow Relaxation in a Two-Dimensional Network of {Mn6} Cages

      Catherine Dendrinou-Samara, James P. S. Walsh, Christopher A. Muryn, David Collison, Richard E. P. Winpenny and Floriana Tuna

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/ejic.201700832

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      A 2D network of covalently linked {Mn2IIIMn4II} entities with two different orientations of their Jahn–Teller axes and complex magnetic behaviour, displaying simultaneously weak ferromagnetism, spin canting, slow magnetic relaxation, metamagnetic behaviour and an unusual reversed hysteresis.

  6. Communications

    1. Alkaline Earth Ion Sensors

      Synthesis, Characterization, and Selective Sr2+ Sensing Study of Copper(I)-Bridged Calix[4]arene-Based Binuclear Alkynylplatinum(II) Complexes

      Yu-Zhe Chen, Dun Pan, Bin Chen, Ge-Xia Wang, Chen-Ho Tung and Li-Zhu Wu

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/ejic.201700672

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      Copper-bridged calix[4]arene-based binuclear alkynylplatinum(II) complexes are designed. The binuclear complex bearing aza[15]crown-5 pendants exhibits a unique emission enhancement at ca. 750 nm toward Sr2+ ions, a result of altering the lowest excited state from the nonemissive ligand-to-ligand charge-transfer (LLCT) state to the emissive metal–metal-to-ligand charge-transfer (MMLCT) state.

  7. Full Papers

    1. Bioimaging

      Luminescent 1,8-Naphthalimide-Derived ReI Complexes: Syntheses, Spectroscopy, X-ray Structure and Preliminary Bioimaging in Fission Yeast Cells

      Emily E. Langdon-Jones, Catrin F. Williams, Anthony J. Hayes, David Lloyd, Simon J. Coles, Peter N. Horton, Lara M. Groves and Simon J. A. Pope

      Version of Record online: 7 SEP 2017 | DOI: 10.1002/ejic.201700549

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      1,8-Naphthalimide-derived, picolyl-based ligands have been coordinated to ReI to form luminescent complexes. The complexes were characterised by using an array of spectroscopic methods, and one example provided an X-ray crystal structure. Selected complexes were explored as fluorescence cell imaging agents by using fission yeast cells.

    2. Iridium Chromophores

      Efficient Phosphorescence from Naphthalenebenzimidizole-Coordinated Iridium(III) Chromophores

      James E. Yarnell, Patricia De La Torre and Felix N. Castellano

      Version of Record online: 7 SEP 2017 | DOI: 10.1002/ejic.201700669

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      Two phosphorescent iridium(III) complexes demonstrate that cyclometalation of the rigid naphthalenebenzimidizole (NBI) ligand onto Ir can impart desirable photophysical properties to the complex, such as visible light absorptivity and high photoluminescence quantum yields. The molecules were investigated using DFT calculations, photoluminescence spectroscopy, and transient absorption spectroscopy.

    3. Magnetic Heterometallic Clusters

      {[Ln(hfac)3]2[Cu(hfac)2]3(NIT-Pyrim)2(H2O)2} (LnIII = Gd, Ho, Er): Unique Nitronyl Nitroxide Bridged 3d–4f Heterometallic Clusters

      Cun Li, Hongdao Li, Jing Xie, Meng Yang, Xiufeng Wang and Licun Li

      Version of Record online: 21 AUG 2017 | DOI: 10.1002/ejic.201700576

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      Three novel 3d–4f pentanuclear clusters linked by pyrimidine-substituted nitronyl nitroxides have been achieved. The nitronyl nitroxide radical behaves as a tridentate ligand. Ferromagnetic couplings are observed between the metal ions and the radical ligands. Furthermore, Ho derivatives exhibit slow magnetic relaxation behavior, which is the first example of a nitronyl nitroxide–Ho-based SMM.

    4. Intramolecular Energy Transfer | Very Important Paper

      An N^N Platinum(II) Bis(acetylide) Complex with Naphthalimide and Pyrene Ligands: Synthesis, Photophysical Properties, and Application in Triplet–Triplet Annihilation Upconversion

      Fangfang Zhong and Jianzhang Zhao

      Version of Record online: 7 AUG 2017 | DOI: 10.1002/ejic.201700656

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      A PtII complex (Pt-NI-Py) with naphthalimide (NI) and pyrene (Py) chromophores as acetylide ligands exhibits a broad absorption band and pyrene-localized room-temperature phosphorescence (ΦP = 4 %). Efficient singlet oxygen generation (ΦΔ = 80 %) and a high quantum yield for triplet–triplet annihilation (TTA) upconversion (ΦUC = 34 %) verify that Pt-NI-Py is a good triplet photosensitizer.

  8. Communications

    1. Phosphorescent Ir Phthalocyanines

      Near Infra-Red S0[LEFT RIGHT ARROW]T1 Transitions of Iridium(III) Phthalocyanine: Degeneracy of the T1 State Evidenced by Magnetic Circular Dichroism

      Kei Murata and Kazuyuki Ishii

      Version of Record online: 2 AUG 2017 | DOI: 10.1002/ejic.201700668

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      The lowest excited triplet (T1) state of an iridium(III) phthalocyanine (IrPc) complex was investigated by electronic absorption, magnetic circular dichroism (MCD), and emission spectroscopy. The Faraday A term was successfully observed for the S0[RIGHTWARDS ARROW]T1 transition in the MCD spectrum, indicating the degeneracy of the T1 state.

    2. Photoinduced Charge Transfer | Very Important Paper

      Probing Transient Photoinduced Charge Transfer in Prussian Blue Analogues with Time-Resolved XANES and Optical Spectroscopy

      Serhane Zerdane, Marco Cammarata, Lodovico Balducci, Roman Bertoni, Laure Catala, Sandra Mazerat, Talal Mallah, Martin N. Pedersen, Michael Wulff, Kosuke Nakagawa, Hiroko Tokoro, Shin-ichi Ohkoshi and Eric Collet

      Version of Record online: 20 JUL 2017 | DOI: 10.1002/ejic.201700657

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      We studied the transient electron-transfer process induced by a femtosecond laser pulse in nanocrystals of CsCoFe and RbMnFe Prussian Blue analogues by time-resolved X-ray absorption near-edge structure and time-resolved optical spectroscopy. The results clearly evidence ultrafast CoIII(low spin)FeII[RIGHTWARDS ARROW]CoII(high spin)FeIII and MnIII(low spin)FeII[RIGHTWARDS ARROW]MnII(high spin)FeIII electron-transfer processes.

  9. Full Papers

    1. Photoinduced Spin Crossover

      On the Effect of the Internal Pressure on the Photoinduced Spin-Crossover Behavior of [FexM1–x(1,10-phenanthroline)2(NCS)2] Solid Solutions (M = NiII, ZnII, and CdII)

      Mame Seyni Sylla, Chérif Baldé, Nathalie Daro, Cédric Desplanches, Mathieu Marchivie and Guillaume Chastanet

      Version of Record online: 30 JUN 2017 | DOI: 10.1002/ejic.201700350

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      The thermal and light-induced magnetic properties of a family of metal-diluted spin-crossover complexes, [FexM1–x(phen)2(NCS)2] (phen = 1,10-phenantholine and M = NiII, CdII), are reported. The dilution has a strong effect on the magnetic and photomagnetic properties.

    2. Heterodimetallic Complexes

      Synthesis, Crystal Structure and Magnetic Properties of Three {CrIIIMnII} Heterodimetallic Complexes Based on Heteroleptic Cyanido-Bearing CrIII Building Blocks

      Maria-Gabriela Alexandru, Diana Visinescu, Beatrice Braun-Cula, Francesc Lloret and Miguel Julve

      Version of Record online: 23 JUN 2017 | DOI: 10.1002/ejic.201700313

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      Two dinuclear {MnIICrIII} and one trinuclear {MnIICr2III} cyanido-bridged complexes were obtained by assembling CrIII metalloligands and preformed MnII complexes. Their magnetic properties indicate predominant AF coupling between CrIII and MnII.

    3. Spin-Crossover Nanoparticles

      Control of the Phase Stability in Spin-Crossover Core–Shell Nanoparticles through the Elastic Interface Energy

      Gautier Félix, Mirko Mikolasek, Gábor Molnár, William Nicolazzi and Azzedine Bousseksou

      Version of Record online: 30 MAY 2017 | DOI: 10.1002/ejic.201700121

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      The phase stability of core–shell spin-crossover nanoparticles was investigated by a continuum mechanics approach. We demonstrate that the transition temperature of a spin-crossover core–shell nanoparticle can be modulated by tuning the elastic misfit, and the associated stress, between the core and the shell. In this way, the memory effect (bistability) can be controlled on the nanoscale.

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