European Journal of Inorganic Chemistry

Cover image for Vol. 2016 Issue 4

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

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.942

ISI Journal Citation Reports © Ranking: 2014: 9/45 (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


  1. 1 - 100
  2. 101 - 116
  1. Microreviews

    1. Hydroelementation

      Hydroelementation of Unsaturated C–C Bonds Catalyzed by Metal Scorpionate Complexes

      Matthew Wathier and Jennifer A. Love

      Article first published online: 5 FEB 2016 | DOI: 10.1002/ejic.201501272

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      A review of recent advances in hydroelementation (E = S, N, O, P) of alkenes and alkynes catalyzed by metal complexes bearing scorpionate-type ligands.

  2. Full Papers

    1. Boron–Sulfur Clusters

      Binary B4S4 Rhombic Clusters as Promising Inorganic Ligands for ­Triple-Decker Sandwich Complexes

      Da-Zhi Li, Shi-Guo Zhang and Chen-Chu Dong

      Article first published online: 5 FEB 2016 | DOI: 10.1002/ejic.201501439

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      The binary B4S4 rhombic cluster possesses a four-membered heteroatomic ring with 4π electrons in a nonbonding/bonding combination, differing from cyclobutadiene. B4S4 (C2v 1A1) is predicted to be an effective inorganic ligand to form triple-decker sandwich-type transition-metal complexes, such as D2h (B4S4)3M2 (M = Ni, Pd, and Pt).

    2. P,N-Heterocycles

      Conformational Analysis of P,N-Containing Eight-Membered Heterocycles and Their Pt/Ni Complexes in Solution

      Shamil Latypov, Anna Strelnik, Anna Balueva, Yulia Spiridonova, Andrey Karasik and Oleg Sinyashin

      Article first published online: 5 FEB 2016 | DOI: 10.1002/ejic.201501331

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      Biligand complexes ([M(PR2NR′2)2]2+, M = Pt, Ni) are in CBCB1 conformation with distortion of the metal coordination plane. Ni complexes have higher distortion and intramolecular exchange barriers than Pt complexes. Bulky P-substituents increase the distortion of the coordination plane and slow down its “twisting” rate. The counterion type also affects the structure and dynamics of these complexes.

    3. Organometallic Copolymers

      Synthesis and Charge–Discharge Properties of Organometallic Co­polymers of Ferrocene and Triphen­ylamine as Cathode Active Materials for Organic-Battery Applications

      Jing Xiang, Kan Sato, Hiroshi Tokue, Kenichi Oyaizu, Cheuk-Lam Ho, Hiroyuki Nishide, Wai-Yeung Wong and Mingdeng Wei

      Article first published online: 5 FEB 2016 | DOI: 10.1002/ejic.201501169

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      Copolymers of ferrocene and triphenylamine (PVFVM1 and PVFVM1-1) show electrochemical characteristics of the ferrocene and triphenylamine pendants with multiple redox waves. PVFVM1 exhibits a discharge capacity of 102 mA h g–1 at 10 C, which corresponds to 98 % of its theoretical capacity.

    4. Intermetallic Compounds

      Sr2Pd4Al5: Synthesis, Crystal and Electronic Structures, and Chemical Bonding of a Polar Intermetallic Compound

      Frank Stegemann, Christopher Benndorf, Rachid St. Touzani, Boniface P. T. Fokwa and Oliver Janka

      Article first published online: 4 FEB 2016 | DOI: 10.1002/ejic.201501455

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      Sr2Pd4Al5 crystallizes in a new structure type that exhibits an interesting bonding situation within the polyanionic [Pd4Al5]δ framework. DFT calculations confirm the crystallographically observed bonding situations and that the compound should be considered polar intermetallic since Sr transfers its electrons mainly onto the palladium atoms.

    5. Metallonucleases

      Photoinduced and Self-Activated Nuclease Activity of Copper(II) Complexes with N-(Quinolin-8-yl)quin­olin-8-sulfonamide – DNA and Bovine Serum Albumin Binding

      Alejandro Pascual-Álvarez, Tamara Topala, Francisco Estevan, Francisca Sanz and Gloria Alzuet-Piña

      Article first published online: 4 FEB 2016 | DOI: 10.1002/ejic.201501469

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      [Cu(QSQ)(phen)]ClO4·0.5H2O (1) and [Cu(QSQ)(phen)(H2O)]ClO4 [2; phen = phenanthroline, HQSQ = N-(quinolin-8-yl)quinolin-8-sulfonamide] are synthesized and physicochemically characterized. Compound 1 performs oxidative DNA cleavage upon photoirradiation in the presence of ascorbate/H2O2 and, interestingly, in the absence of any external reagent.

    6. Gold-Mediated Isomerizations

      Gold-Mediated Isomerization of ­Cyclooctyne to Ring Fused Olefinic Bicycles

      Animesh Das, Yuanda Hua, Muhammed Yousufuddin, Thomas R. Cundari, Junha Jeon and H. V. Rasika Dias

      Article first published online: 4 FEB 2016 | DOI: 10.1002/ejic.201600021

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      Gold catalyzes the isomerization of cyclooctyne leading to alkenes featuring two fused five-membered rings.

    7. Oligosilsesquioxanes

      Mechanism and Kinetics of Oligosilsesquioxane Growth in the In Situ Water Production Sol–Gel Route: Dependence on Water Availability

      Evgeny Borovin, Emanuela Callone, Francois Ribot and Sandra Diré

      Article first published online: 4 FEB 2016 | DOI: 10.1002/ejic.201501220

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      Small thiol-functionalized oligosilsesquioxanes were prepared by the in situ water production (ISWP) process in which water was homogenously generated by an esterification reaction. Manipulation of the temperature allowed the water production kinetics to be controlled, which played a major role on the degree of condensation (DOC) of the formed nanobuilding blocks.

  3. Communications

    1. Supported Nanoparticles

      You have full text access to this OnlineOpen article
      Gold Nanoparticle@Polyhedral Oligomeric Silsesquioxane Hybrid Scaffolds in Microfluidic Format – Highly Efficient and Green Catalytic Platforms

      Pascal Scholder, Martina Hafner, Achim W. Hassel and Ivo Nischang

      Article first published online: 4 FEB 2016 | DOI: 10.1002/ejic.201501376

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      Hybrid organic–inorganic porous monolithic materials were prepared in situ in small conduits. Their internal structure is decorated with gold nanoparticles anchored by pendant thiol groups through thiol–gold interactions. The materials are efficient catalysts, and their repeated use under continuous flow catalysis conditions results in no loss of performance, which indicates their robustness.

  4. Full Papers

    1. Thermoelectric Materials

      Thermoelectric Properties of Ni0.05Mo3Sb5.4Te1.6 with Embedded SiC and Al2O3 Nanoparticles

      Nagaraj Nandihalli, Quansheng Guo, Stéphane Gorsse, Atta Ullah Khan, Takao Mori and Holger Kleinke

      Article first published online: 3 FEB 2016 | DOI: 10.1002/ejic.201501063

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      Nanocomposites of Ni0.05Mo3Sb5.4Te1.6 with embedded SiC and Al2O3 nanoparticles are introduced. The nanoadditions lower the thermal and electrical conductivities to different extents, ultimately resulting in enhanced thermoelectric performance (ZT) on addition of small amounts of SiC. A more substantial enhancement was achievement by spark-plasma-sintering instead of hot-pressing.

  5. Communications

    1. Agostic Interactions

      Enhancing Reactivity of Directly ­Observable B–H–Pt Interactions through Conformational Rigidity

      Shrinwantu Pal, Marcus W. Drover, Brian O. Patrick and Jennifer A. Love

      Article first published online: 3 FEB 2016 | DOI: 10.1002/ejic.201501305

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      Trimethylplatinum(IV) complexes featuring agostic B–H–Pt interactions supported by bis(pyrazolyl)borate (Bp) and bis(3,5-dimethylpyrazolyl)borate (Bp*) ligands show interesting structural differences both in solution and the solid state. These differences result in enhanced reactivity of the Bp* complexes towards hydroboration of acetonitrile and protonolysis with methanol.

  6. Full Papers

    1. Non-Heme Iron Complexes

      Mimicry of the 2-His-1-Carboxylate Facial Triad Using Bulky N,N,O-Ligands: Non-Heme Iron Complexes Featuring a Single Facial Ligand and Easily Exchangeable Co-Ligands

      Emma Folkertsma, Esther F. de Waard, Gerda Korpershoek, Arnoldus J. van Schaik, Naiara Solozabal Mirón, Mandy Borrmann, Sjoerd Nijsse, Marcel A. H. Moelands, Martin Lutz, Matthias Otte, Marc-Etienne Moret and Robertus J. M. Klein Gebbink

      Article first published online: 2 FEB 2016 | DOI: 10.1002/ejic.201501406

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      Mononuclear iron(II) complexes with a single facially coordinating N,N,O-ligand were synthesized as accurate structural mimics of the 2-His-1-carboxylate facial triad found in mononuclear non-heme iron enzymes. The new [FeLOTfn] complexes provide three readily available coordination sites and show catalytic activity in epoxidation reactions.

    2. OLEDs

      Two Green-Phosphorescent Iridium Complexes with 2-Phenylpyrimidine Derivatives and Tetraphenylimido­diphosphinate for Efficient Organic Light-Emitting Diodes

      Song Zhang, Jing-Cheng Xia, Zheng-Guang Wu, Guang-Zhao Lu, Yue Zhao and You-Xuan Zheng

      Article first published online: 2 FEB 2016 | DOI: 10.1002/ejic.201501318

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      Organic light-emitting diodes (OLEDs) based on IrIII complexes containing pyrimidine derivatives as cyclometalated ligands and tetraphenylimidodiphosphinate as ancillary ligand exhibited maximum current efficiencies as high as 81.91 and 71.17 cd A–1 and maximum external quantum efficiencies of 20.8 and 21.3 %, respectively, with low-efficiency roll-off.

    3. Photoactive Anticancer Compounds

      Mitochondria-Targeting Iron(III) Catecholates for Photoactivated Anticancer Activity under Red Light

      Uttara Basu, Ila Pant, Paturu Kondaiah and Akhil R. Chakravarty

      Article first published online: 2 FEB 2016 | DOI: 10.1002/ejic.201501105

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      Iron(III) catecholates bearing anthracenyl or pyrenyl groups and a dipicolylamine base with a cationic triphenylphosphonium (TPP) moiety show remarkable photocytotoxicity under red light, mitochondrial localization, reactive oxygen species (ROS) generation, and apoptotic cell death. They showed significant DNA photocleavage activity under red light (785 nm), forming hydroxyl radicals as the ROS.

  7. Microreviews

    1. Metallacycles

      Bis(pyrazol-1-yl)(pyridin-x-yl)methane Ligands – Mono- or Ditopic Ligands in Complexes and Supramolecular Frameworks

      Blanca R. Manzano, Félix A. Jalón, M. Carmen Carrión and Gema Durá

      Article first published online: 1 FEB 2016 | DOI: 10.1002/ejic.201501271

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      Bis(pyrazol-1-yl)(pyridin-x-yl)methane ligands give rise to a rich variety of complexes and supramolecular frameworks with a wide range of transition metals. With x = 2, the ligands behave as monotopic, usually with tripodal coordination, whereas with x = 3 or 4 they act as bridges, giving rise to polymers or dinuclear or trinuclear discrete species.

  8. Communications

    1. Heteroallene Activation

      Activation of Heteroallenes COxS2–x (x = 0–2): Experimental and Theoretical Evidence of the Synthetic Versatility of a Bulky Guanidinato SmII Complex

      Ludovic Castro, David P. Mills, Cameron Jones and Laurent Maron

      Article first published online: 1 FEB 2016 | DOI: 10.1002/ejic.201501346

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      A combined experimental/DFT study of the activation of COxS2–x (x = 0–2) by [Sm(Giso)2] is reported. Activation of CS2 yields a bimetallic CS2 coupled product. CO2 forms an oxalate complex through C–C bond formation, which then undergoes CO2 insertion into one of its Sm–N bonds. COS activation is predicted to yield a dithiocarbonate complex, through the formation of an intermediate sulfido complex.

    2. Uranyl Clusters

      Dynamic Phosphonic Bridges in Aqueous Uranyl Clusters

      Anna F. Oliveri, Corey D. Pilgrim, Jie Qiu, Christopher A. Colla, Peter C. Burns and William H. Casey

      Article first published online: 1 FEB 2016 | DOI: 10.1002/ejic.201600036

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      The phosphonic bridges in the uranyl cage clusters U22 and U28 have been monitored in aqueous solutions using the unique combination of 1H DOSY and 1H-31P HSQC spectroscopy. The hydrodynamic radii of these clusters are measured to be 9.8 ± 0.4 Å (U22) and 12.3 ± 0.5 Å for the (U28) in D2O. Relating specific sites in the structures of these clusters to NMR signals reveals the presence of phosphonic-bridge conformers.

  9. Full Papers

    1. Pyrochlore Nanoparticles

      Synthesis of Bi–Fe–Sb–O Pyrochlore Nanoparticles with Visible-Light Photocatalytic Activity

      Anna V. Egorysheva, Olga M. Gajtko, Pavel O. Rudnev, Olga G. Ellert and Vladimir K. Ivanov

      Article first published online: 1 FEB 2016 | DOI: 10.1002/ejic.201501159

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      Bi–Fe–Sb–O pyrochlore nanoparticles are synthesized by microwave hydrothermal treatment. The samples consist of 100–200 nm spherical agglomerates formed from 20 nm mutually oriented nanocrystallites. Some of the spheres are hollow. The photocatalytic activity of the pyrochlore nanoparticles is higher than that of TiO2.

    2. Organometallic Lead Chemistry

      The Reactivity of Diphenyllead(IV) Dichloride with Dissymmetric Thiosemicarbazone Ligands: Obtaining Monomers, Coordination Polymers, and an Organoplumboxane

      Ester Sesmero, David G. Calatayud, Josefina Perles, Elena López-Torres and M. Antonia Mendiola

      Article first published online: 1 FEB 2016 | DOI: 10.1002/ejic.201501245

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      The reaction of PbPh2Cl2 with dissymmetric thiosemicarbazones strongly depends on the reaction conditions and leads to seven new compounds, including mononuclear complexes, coordination polymers, and an organoplumboxane, which, to the best of our knowledge, represents the first example of this kind of compound that has been crystallographically characterized.

    3. Layered Hydroxides

      Pseudomorphic Transformation of Layered Simple Hydroxides into Prussian Blue Analogue Nanoplatelets

      Marina Lang, Emilie Delahaye, Dominique Foix, Dris Ihiawakrim, Ovidiu Ersen, Cédric Leuvrey, Jean-Marc Grenèche, Guillaume Rogez and Pierre Rabu

      Article first published online: 1 FEB 2016 | DOI: 10.1002/ejic.201501338

      Thumbnail image of graphical abstract

      Prussian Blue analogue nanoplatelets have been produced by pseudomorphic replication of layered Cu2(OH)3(OAc) in the presence of K4[Fe(CN)6]. A transformation mechanism is proposed. Our results demonstrate that lamellar simple hydroxides can be used as precursors of molecular-based networks and that the lamellar nature of the Cu reservoir favours the organization of crystallites into sheets.

  10. Communications

    1. Microwave Synthesis

      Synthesis of Hexagonal-Phase Eu3+-Doped GdF3 Nanocrystals above Room Temperature by Controlling the Viscosity of the Solvents

      Tuhin Samanta, Chanchal Hazra, Athma E. Praveen, Sagar Ganguli and Venkataramanan Mahalingam

      Article first published online: 29 JAN 2016 | DOI: 10.1002/ejic.201501146

      Thumbnail image of graphical abstract

      The synthesis of hexagonal-phase GdF3 nanocrystals at higher temperatures has been achieved by controlling the viscosity of the solvents used. Highly luminescent hexagonal-phase Eu3+-doped GdF3 nanocrystals were prepared above 200 °C.

  11. Communication

    1. Polyoxometalates

      An Easy Way to Construct Polyoxovanadate-Based Organic–Inorganic Hybrids by Stepwise Functionalization

      Zicheng Xiao, Kun Chen, Baolin Wu, Wenjing Li, Pingfan Wu and Yongge Wei

      Article first published online: 29 JAN 2016 | DOI: 10.1002/ejic.201501297

      Thumbnail image of graphical abstract

      A step-by-step functionalization methodology has been developed for the construction of complicated polyoxovanadate hybrids, and a series of novel functionalized polyoxovanadates have been synthesized by esterification and amidation reactions in a convenient and efficient way.

  12. Full Papers

    1. Layered Compounds

      Phase Relations and Physical Properties of Layered Pb-Containing Nd2MoO6 Compounds

      Valentina Voronkova, Ekaterina Orlova, Sergey Kazakov, Elena Kharitonova and Dmitry Belov

      Article first published online: 29 JAN 2016 | DOI: 10.1002/ejic.201501167

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      We report herein the synthesis, XRD characterization, and electrical properties of new lead-containing layered molybdates based on Nd2MoO6. In contrast to pure Nd2MoO6, these materials reveal first-order reversible phase transitions accompanied by dielectric anomalies, DSC events, and sharp jumps in conductivity. The conductivity reaches 10–2 S/cm at 850 °C and may be due to oxygen ions.

    2. Characterizing Radicals

      Bipyridinium-bis(carboxylate) Radical Based Materials: X-ray, EPR and Paramagnetic Solid-State NMR Investigations

      Oksana Toma, Maxime Leroux, Nicolas Mercier, Magali Allain, Abdel Hadi Kassiba, Shashi Kumar Kumara Swamy and Jens Dittmer

      Article first published online: 29 JAN 2016 | DOI: 10.1002/ejic.201501206

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      Crystals of a bipyridinium-bis(carboxylate) ligand (bp4pc) have been synthesized in both the protonated reduced form and in the hydrated form. Upon heating, partial dehydration of the latter phase is accompanied by an electron-transfer process, resulting in the colored bp4pc· radical, as revealed by solid-state NMR spectroscopy.

    3. C–C Coupling Catalysts

      The Influence of Imidazolylidene Ligands with Bulky Resorcinarenyl Substituents on Catalysts for ­Suzuki–Miyaura Coupling

      Murat Kaloğlu, David Sémeril, Eric Brenner, Dominique Matt, İsmail Özdemir and Loïc Toupet

      Article first published online: 29 JAN 2016 | DOI: 10.1002/ejic.201501238

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      A palladium complex containing a bulky N-heterocyclic carbene ligand having one of its nitrogen atoms substituted by an extended cavitand, showed high efficiency in Suzuki–Miyaura cross-coupling of aryl chlorides with sterically hindered arylboronic acids.

    4. Heterometallic Coordination Polymers

      A Series of Copper–Lanthanide Heterometallic Coordination Polymers Derived from Pyridine-2,3-dicarboxylic Acid and in situ Generated Succinic Acid

      Ju-Wen Zhang, Xiao-Min Kan, Xiao-Li Li, Ying Liu and Bin-Qiu Liu

      Article first published online: 29 JAN 2016 | DOI: 10.1002/ejic.201501328

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      A series of copper–lanthanide heterometallic coordination polymers (CPs) with three types of 3D frameworks and two structural critical points have been successfully synthesized and structurally characterized. The dysprosium-containing CP shows a field-induced slow magnetic relaxation behavior.

    5. Metal–Organic Frameworks

      Hole-Size Relationships in the Assembly of a Furandicarboxylate-Based Metallolinker in Praseodymium Coordination Polymers Synthesized under Basic Conditions

      Jeffrey D. Einkauf, Joseph P. Karram, Natalie E. Greig, Benny C. Chan and Daniel T. de Lill

      Article first published online: 29 JAN 2016 | DOI: 10.1002/ejic.201501350

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      Two new coordination polymers have been hydrothermally synthesized with 2,5-furandicarboxylic acid. The structures are dependent upon the base added. KI ions from KOH produce a metallolinker, whereas other bases did not result in metallolinker formation. Crystallographic analyses indicate that metallolinker formation is highly size-dependent.

    6. Iron Scorpionate Complexes

      Mononuclear Iron-(hydro/semi)­quinonate Complexes Featuring Neutral and Charged Scorpionates: Synthetic Models of Intermediates in the Hydroquinone Dioxygenase Mechanism

      Amanda E. Baum, Sergey V. Lindeman and Adam T. Fiedler

      Article first published online: 29 JAN 2016 | DOI: 10.1002/ejic.201501380

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      Both neutral and anionic scorpionates are used to prepare synthetic models of hydroquinone dioxygenases (HQDOs) – a class of mononuclear nonheme enzymes. The different ligands mimic variations in coordination geometry within the HQDO family. The ferric-hydroquinonate complexes undergo reversible deprotonation to yield ferrous-semiquinonate species.

    7. Ruthenium Catalysts

      Synthesis, Structural Characterization, and Catalytic Activity of Indenyl Tris(N-pyrrolyl)phosphine Complexes of Ruthenium

      Matthew J. Stark, Michael J. Shaw, Nigam P. Rath and Eike B. Bauer

      Article first published online: 29 JAN 2016 | DOI: 10.1002/ejic.201501381

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      The ruthenium tris(N-pyrrolyl)phosphine [P(pyr)3] complexes [RuCl(ind)(PPh3){P(pyr)3}] and [RuCl(ind){P(pyr)3}2] exhibit increased oxidation potentials owing to the π-acidic P(pyr)3 ligands. The complexes are catalytically active in the etherification of propargylic alcohols and in the formation of known and new xanthenones from propargylic alcohols and diketones.

  13. Microreviews

    1. Green Synthesis

      Green Synthesis of Inorganic-Organic Hybrid Materials: State of the Art and Future Perspectives

      Miriam M. Unterlass

      Article first published online: 29 JAN 2016 | DOI: 10.1002/ejic.201501130

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      Inorganic–organic hybrids combine, for example, the mechanical and temperature stability of inorganic colloids with the light weight and processability of organic polymers. For their green synthesis, one has to combine benign approaches towards both constituents. This microreview summarizes green syntheses of both components and reviews the implementation of green chemistry for hybrid materials.

    2. s-Block Complexes

      s-Block Metal Complexes with Bis- and Tris(pyrazolyl)methane and -methanide Ligands

      Sven Krieck, Alexander Koch, Kay Hinze, Christoph Müller, Juliane Lange, Helmar Görls and Matthias Westerhausen

      Article first published online: 29 JAN 2016 | DOI: 10.1002/ejic.201501263

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      Deprotonation of substituted tris(pyrazolyl)methanes yields the corresponding tris(pyrazolyl)methanides, which show diverse coordination modes and susceptibility to degradation in the vicinity of heavy s-block metals, depending on the substitution pattern of the pyrazolyl rings.

    3. Electron Microscopy

      You have full text access to this OnlineOpen article
      What Can Electron Microscopy Tell Us Beyond Crystal Structures?

      Wuzong Zhou and Heather F. Greer

      Article first published online: 27 JAN 2016 | DOI: 10.1002/ejic.201501342

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      Some examples of conventional SEM and TEM studies of inorganic crystals are reviewed. Typical problems of misinterpretation of the images are discussed.

  14. Full Papers

    1. Dye-Sensitized Solar Cells

      Ferrocenyl Dithiocarbamate Based d10 Transition-Metal Complexes as Potential Co-Sensitizers in Dye-Sensitized Solar Cells

      Reena Yadav, Manoj Trivedi, Gabriele Kociok-Köhn, Ratna Chauhan, Abhinav Kumar and Suresh W. Gosavi

      Article first published online: 27 JAN 2016 | DOI: 10.1002/ejic.201501449

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      Three new d10 transition-metal dithiocarbamates containing ferrocene have been synthesized and their application as co-sensitizers to the state-of-the-art dye N719 in dye-sensitized solar cells explored.

    2. Thermally Stable Explosives

      (Picrylamino)-1,2,4-triazole Derivatives – Thermally Stable Explosives

      Zoe L. Chioato, Thomas M. Klapötke, Frank Mieskes, Jörg Stierstorfer and Michael Weyrauther

      Article first published online: 27 JAN 2016 | DOI: 10.1002/ejic.201501435

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      New energetic and highly thermally stable salts of 3-(picrylamino)-1,2,4-triazole (PATO) and 3-amino-5-(picrylamino)-1,2,4-triazole (APATO) are synthesized. PATO shows high thermal stability with good energetic performance as a highly thermally stable explosive. The ammonium salt of PATO also shows promising energetic performance with a slightly lower thermal stability than that of neutral PATO.

    3. Reactivity on Deprotonation

      Reactivity of Me-pma RhI and IrI Complexes upon Deprotonation and Their Application in Catalytic Carbene Carbonylation Reactions

      Zhou Tang, Cristina Tejel, Marc Martinez de Sarasa Buchaca, Martin Lutz, Jarl Ivar van der Vlugt and Bas de Bruin

      Article first published online: 27 JAN 2016 | DOI: 10.1002/ejic.201501302

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      The coordination chemistry of group 9 metals with a novel redox-noninnocent picolyl-amine-based ligand is elucidated through combined NMR spectroscopy and X-ray structure determination. The ability of these ligands to form both mono- and dinuclear metal complexes illustrates the versatile nature of such ligands. The mononuclear Rh complex is active in carbene carbonylation to generate ketenes.

    4. Doped Titania

      Structural and Magnetic Properties of 57Fe-Doped TiO2 and 57Fe/Sn-Codoped TiO2 Prepared by a Soft-Chemical Process

      Yanjie Wang, Kiyoshi Nomura, Xin Liu, Alexandre I. Rykov, Changzi Jin, Tao Liu and Junhu Wang

      Article first published online: 27 JAN 2016 | DOI: 10.1002/ejic.201501173

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      Room-temperature ferromagnetism (RTFM) was found in 57Fe-TiO2 and 57Fe/Sn-TiO2 materials prepared by a soft-chemical solution method. Their magnetic properties were found to decrease with increasing degree of 57Fe doping. Fe3+–oxygen vacancy (VO)–Fe3+ centers are responsible for the observed RTFM.

    5. Heterodimetallic Compounds

      A Periodic Walk through a Series of First-Row, Oxido-Bridged, Heterodimetallic Molecules: Synthesis and Structure

      Eric M. Goggins, Travis T. Lekich, Walter W. Weare, Roger D. Sommer, Marco A. Ribeiro and Carlos B. Pinheiro

      Article first published online: 26 JAN 2016 | DOI: 10.1002/ejic.201501325

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      By using a Lewis-basic Ti=O group, a series of oxido-bridged heterodimetallic molecules comprised of earth-abundant first-row elements is described. By varying the metal identity of the Lewis-acidic center, molecular properties such as bridge stability and redox potentials can be tuned.

    6. Gold Nanoparticles

      Molecular and Electronic Structure of the Cluster [Au8(PPh3)8](NO3)2

      Benjamin S. Gutrath, Frank Schiefer, Melanie Homberger, Ulli Englert, Mihaela-D. Şerb, Wolfgang Bettray, Igor Beljakov, Velimir Meded, Wolfgang Wenzel and Ulrich Simon

      Article first published online: 25 JAN 2016 | DOI: 10.1002/ejic.201501334

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      A detailed structural characterization together with an experimental (optical extinction spectroscopy, luminescence spectroscopy, voltammetry) and DFT-based analysis of the electronic structure of the triphenylphosphine-stabilized cluster [Au8(PPh3)8](NO3)2 gives an insight into structure–property relationships.

    7. Lanthanide Complexes

      Lanthanide Complexation of 2,6-Bis(5,6-dipyridyl-1,2,4-triazinyl)pyr­idine – Solvent- and Lanthanide-Ion-Controlled Ligand Coordination Mode and Denticity

      Arunasis Bhattacharyya, Paul M. Forster, Daniel B. Rego and Kenneth R. Czerwinski

      Article first published online: 25 JAN 2016 | DOI: 10.1002/ejic.201501382

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      Solvent- and metal-ion-dependent changes in the ligand coordination mode and denticity in the lanthanide complexes of 2,6-bis(5,6-dipyridyl-1,2,4-triazinyl)pyridine (PyBTP) are investigated through fluorescence spectroscopy, 1H NMR spectroscopy, UV/Vis spectrophotometry, attenuated total reflectance (ATR) FTIR spectroscopy, and single-crystal XRD.

    8. Ring-Opening Polymerization

      Synthesis and Dynamic Behavior of Chiral NNO-Scorpionate Zinc Initiators for the Ring-Opening Polymerization of Cyclic Esters

      Manuel Honrado, Antonio Otero, Juan Fernández-Baeza, Luis F. Sánchez-Barba, Andrés Garcés, Agustín Lara-Sánchez and Ana M. Rodríguez

      Article first published online: 22 JAN 2016 | DOI: 10.1002/ejic.201501347

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      A new series of chiral dinuclear trisalkyl- and alkyl–aryl oxide-containing zinc heteroscorpionates complexes, namely, [Zn(R)(κ2-NNµ-O)Zn(R)2] and [(ZnR)2(κN:κN-µ-O)(µ-OAr)], respectively, has been synthesized. Their dynamic behavior has been studied. Both families act as single-component living initiators for the ring-opening polymerization of ϵ-CL and L-/rac-LA.

    9. Heterocubanes

      Controlled Synthesis of Pnicogen–Chalcogen Polycations in Ionic Li­quids

      Matthias F. Groh, Anna Isaeva, Ulrike Müller, Paul Gebauer, Maximilian Knies and Michael Ruck

      Article first published online: 22 JAN 2016 | DOI: 10.1002/ejic.201501430

      Thumbnail image of graphical abstract

      Heteropolycations: Three new pnicogen–chalcogen polycations were synthesized in imidazolium-based Lewis-acidic ionic liquids (IL) at moderate temperatures. Bi2S3, usually soluble only under harsh conditions, readily dissolves and reacts in the employed IL to give a quaternary polycation. The choice of starting materials and the reaction temperature were identified as important control parameters.

  15. Microreviews

    1. Rare-Earth Clusters

      Rare-Earth Metal Oxo/Hydroxo Clusters – Synthesis, Structures, and Applications

      Anna T. Wagner and Peter W. Roesky

      Article first published online: 22 JAN 2016 | DOI: 10.1002/ejic.201501281

      Thumbnail image of graphical abstract

      The synthesis and the structures of rare-earth metal oxo/hydroxo clusters are reviewed. The clusters are very robust, which makes them ideal materials for further chemical, physical, and biological studies.

  16. Full Papers

    1. Abnormal NHC–Borane Adducts

      Abnormal N-Heterocyclic-Carbene-Mediated Fixation of CO2 and N2O, and the Activation of Tetrahydro­furan and Tetrahydrothiophene under Ambient Conditions

      Arunabha Thakur, Pavan K. Vardhanapu, Gonela Vijaykumar, Pradip Kumar Hota and Swadhin K. Mandal

      Article first published online: 22 JAN 2016 | DOI: 10.1002/ejic.201501303

      Thumbnail image of graphical abstract

      The abnormal N-heterocyclic carbene, 1,3-bis(2,6-diisopropylphenyl)-2,4-diphenylimidazole-5-ylidene, reacts with B(C6F5)3 in the presence of CO2 or N2O to form [aNHC·CO2·B(C6F5)3] or [aNHC·N2O·B(C6F5)3], respectively, in high yields at room temperature within a very short period of time.

    2. Azaphospholes

      Synthesis of a Luminescent Azaphosphole

      Shanshan Wu, Arnold L. Rheingold, James A. Golen, Alexandra B. Grimm and John D. Protasiewicz

      Article first published online: 21 JAN 2016 | DOI: 10.1002/ejic.201501279

      Thumbnail image of graphical abstract

      A carbazole-based azaphosphole (compound 3) has been prepared by acid-catalyzed dehydrocyclization of 1-phosphino-9H-carbazole (2) with benzoyl chloride. Compounds 2 and 3 display significant fluorescence in solution.

    3. Hydride Half-Sandwich Complexes

      Reactivity of Hydride Half-Sandwich Ruthenium(II) Complexes Bearing the Scorpionate Ligands Hydridotris(pyrazol-1-yl)borate and Tris(pyrazol-1-yl)methanesulfonate

      Almudena García-Fernández, Sara Miguel, Josefina Díez, Maria Pilar Gamasa and Elena Lastra

      Article first published online: 21 JAN 2016 | DOI: 10.1002/ejic.201501247

      Thumbnail image of graphical abstract

      The hydride complexes [RuH{κ3(N,N,N)-Tp}(PPh3)(pta)] and [RuH{κ3(N,N,N)-Tpms}(pta)2] react with alkynes to form neutral alkenyl complexes. The complex [RuH{κ3(N,N,N)-Tp}(PPh3)(pta)] also reacts with HBF4 to give [Ru(FBF3){κ3(N,N,N)-Tp}(PPh3)(pta)]. A new ruthenium complex bearing a κ2(N,N)-Tpms ligand has been isolated and fully characterized.

    4. Heterogeneous Photocatalysts

      Facile Preparation of AgI/Bi2MoO6 Heterostructured Photocatalysts with Enhanced Photocatalytic Activity

      Ming Xu and Wei-De Zhang

      Article first published online: 20 JAN 2016 | DOI: 10.1002/ejic.201501260

      Thumbnail image of graphical abstract

      Bi2MoO6 microspheres were modified by loading AgI nanoparticles on their surfaces by a facile deposition/precipitation approach. The AgI/Bi2MoO6 heterostructured photocatalysts exhibit high photocatalytic activities and high stabilities towards the degradation of rhodamine B and bisphenol A.

    5. Organouranium Chemistry

      Expanding the Family of Uranium(III) Alkyls: Synthesis and Characterization of Mixed-Ligand Derivatives

      Ellen M. Matson, John J. Kiernicki, Phillip E. Fanwick and Suzanne C. Bart

      Article first published online: 20 JAN 2016 | DOI: 10.1002/ejic.201501251

      Thumbnail image of graphical abstract

      The generation of uranium(III) monoiodide and alkyls supported by both hydrotris(pyrazolyl)borate (Tp) and pentamethylcyclopentadienyl (Cp*) ligands is reported.

    6. Chiral Cryptophanes

      The Stereoselective Self-Assembly of Chiral Metallo-Organic Cryptophanes

      Astrid Schaly, Yoann Rousselin, Jean-Claude Chambron, Emmanuel Aubert and Enrique Espinosa

      Article first published online: 19 JAN 2016 | DOI: 10.1002/ejic.201501446

      Thumbnail image of graphical abstract

      The reactions of racemic cyclotricyanotribenzylene (1) and cyclotricyanotrianisylene (2) with [M(dppp)][OTf]2 (M = Pd or Pt; dppp = 1,3-bisdiphenylphosphinopropane, OTf = triflate) in 2:3 ratios afford the anti forms of the cryptophanes [M3(1)2(dppp)3][OTf]6 and [M3(2)2(dppp)3][OTf]6 stereoselectively. The assemblies of 1 encapsulate CHCl3 molecules in the solid state.

    7. C–H Activation

      Allylic C–H Activation of Olefins by a TpMe2IrIII Compound

      Crispín Cristóbal, Laura L. Santos, Rubén Gutiérrez-González, Eleuterio Álvarez, Margarita Paneque and Manuel L. Poveda

      Article first published online: 19 JAN 2016 | DOI: 10.1002/ejic.201501253

      Thumbnail image of graphical abstract

      The IrIII complex [TpMe2Ir(C6H5)2(N2)] [TpMe2 = hydridotris(3,5-dimethylpyrazolyl)borate] reacts with different olefins to yield organometallic compounds that derive from allylic C–H activations in processes that also generate organic coupling products that involve the vinylic positions of the olefin.

    8. MOF Guest Dynamics

      Multiple Modes of Motion: Realizing the Dynamics of CO Adsorbed in M-MOF-74 (M = Mg, Zn) by Using Solid-State NMR Spectroscopy

      Bryan E. G. Lucier, Hendrick Chan, Yue Zhang and Yining Huang

      Article first published online: 19 JAN 2016 | DOI: 10.1002/ejic.201501242

      Thumbnail image of graphical abstract

      CO dynamics in M-MOF-74 (M = Mg, Zn) are comprehensively described. There are two types of CO motion: a localized sixfold wobbling and a non-localized sixfold hopping. The wobbling angles are inversely proportional to CO heats of adsorption. CO and CO2 motional data in MOF-74 confirm that the wobbling angle of these guests is very sensitive to several factors.

    9. Layered Double Hydroxides

      Amino Acid Interleaved Layered Double Hydroxides as Promising Hybrid Materials for AA2024 Corrosion Inhibition

      Thomas Stimpfling, Pierre Vialat, Horst Hintze-Bruening, Patrick Keil, Viacheslav Shkirskiy, Polina Volovitch, Kevin Ogle and Fabrice Leroux

      Article first published online: 19 JAN 2016 | DOI: 10.1002/ejic.201501161

      Thumbnail image of graphical abstract

      An assembly composed of L-cysteine (L-Cys) intercalated into a layered double hydroxide (LDH) is used as an ion-exchange inorganic functionalized filler dispersed in an epoxy-based primer layer. Upon corrosion, L-Cys molecules are released from the LDH container either by anion exchange or platelet dissolution and retard the corrosion of aluminum alloy AA2024 efficiently.

    10. Red-Emitting Phosphors

      Ca9Sc(PO4)7:Ce3+,Mn2+ – A Red-Emitting Phosphor Based on Energy Transfer

      Hai-Feng Li, Yong-Lei Jia, Teng-Fei Ma, Ran Pang, Wen-Zhi Sun, Da Li, Ji-Peng Fu, Su Zhang, Li-Hong Jiang and Cheng-Yu Li

      Article first published online: 19 JAN 2016 | DOI: 10.1002/ejic.201501099

      Thumbnail image of graphical abstract

      A phosphor with a broad, deep-red emission, Ca9Sc(PO4)7:0.02Ce3+,0.1Mn2+ (CSP:0.02Ce3+,0.1Mn2+), was prepared by energy transfer from Ce3+ to Mn2+ through a dipole–dipole interaction. CSP:Ce3+,Mn2+ phosphors excited at 254 nm emit light in two bands: one at around 360 nm, assigned to the 5d1–4f1 transition of Ce3+, and the other at about 650 nm, derived from the 4T1 (4G) [RIGHTWARDS ARROW] 6A1 (6S) transition of Mn2+.

    11. Single-Molecule Magnets

      A Family of Double Cubanes {CrIII2LnIII4O6} (Ln = Tb, Ho, Er, Yb, Y) Based on Sulfate: Single-Molecule Magnet Behavior in the Terbium and Erbium Analogues

      Hua Xiang, Wen-Guan Lu, Long Jiang, Wei-Xiong Zhang and Yanhua Lan

      Article first published online: 18 JAN 2016 | DOI: 10.1002/ejic.201501285

      Thumbnail image of graphical abstract

      A family of double-cubane Cr2Ln4 compounds was obtained from polydentate inorganic ligand sulfate ions. Single-molecule magnet behavior was observed in the Tb and Er analogues.

    12. Immobilized Catalysts

      Facile Synthesis of Cooperative Acid–Base Catalysts by Clicking Cysteine and Cysteamine on an Ethylene-Bridged Periodic Mesoporous Organosilica

      Judith Ouwehand, Jeroen Lauwaert, Dolores Esquivel, Kevin Hendrickx, Veronique Van Speybroeck, Joris W. Thybaut and Pascal Van Der Voort

      Article first published online: 15 JAN 2016 | DOI: 10.1002/ejic.201501179

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      An ethylene-bridged periodic mesoporous organosilica was functionalized with cysteine and cysteamine by means of thiol-ene click chemistry. The resulting cooperative acid–base catalysts were tested for their activity in an aldol reaction. The influence of the acid promoting sites as well as the loading of the active centers is discussed herein.

    13. Photocatalysts

      Optimized Design of Pt-Doped Bi2WO6 Nanoparticle Synthesis for Enhanced Photocatalytic Properties

      Marie-Anne Lavergne, Corinne Chanéac, David Portehault, Sophie Cassaignon and Olivier Durupthy

      Article first published online: 15 JAN 2016 | DOI: 10.1002/ejic.201501208

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      We discuss the way to prepare optimized metal/oxide nanoheterostructures for photocatalytic applications. The characteristics of the materials are linked to both the mode of metal reduction and the amount deposited. The Rhodamine B photodegradation mechanism and overall rate of degradation are directly impacted by the mode of preparation.

    14. Magnetic Nanoparticles

      Hydrophilic Fe3O4@C for High-­Capacity Adsorption of 2,4-Dichloro­phenol

      Lingzhi Wang, Kaifeng Gan, Deli Lu and Jinlong Zhang

      Article first published online: 15 JAN 2016 | DOI: 10.1002/ejic.201501215

      Thumbnail image of graphical abstract

      The magnetic removal of 2,4-dichlorophenol with a high and stable efficiency over a wide pH range is achieved by hydrophilic Fe3O4@C and is attributed to π–π electron donor–acceptor interactions between Fe3O4@C and 2,4-dichlorophenol, which have electron-rich and electron-deficient π systems, respectively.

    15. Chain Compounds

      Preparation, First Structure Analysis, and Magnetism of the Long-Known Nickel Benzoate Trihydrate – A Linear Ni···Ni···Ni Polymer and Its Parallels with the Active Site of Urease

      Anna Vráblová, Larry R. Falvello, Javier Campo, Jozef Miklovič, Roman Boča, Juraj Černák and Milagros Tomás

      Article first published online: 15 JAN 2016 | DOI: 10.1002/ejic.201501255

      Thumbnail image of graphical abstract

      Nickel benzoate trihydrate (1) has been prepared in single-crystalline form by the reaction of nickel carbonate with benzoic acid in boiling aqueous solution. Its crystal structure and magnetic properties have been determined and are discussed.

    16. Photophysical Properties

      Emissive Ruthenium–Bisdiimine Complexes with Chelated Thioether Donors

      Joachim Hedberg Wallenstein, Jonas Sundberg, Christine J. McKenzie and Maria Abrahamsson

      Article first published online: 15 JAN 2016 | DOI: 10.1002/ejic.201501256

      Thumbnail image of graphical abstract

      Ru–polypyridyl complexes with bidentate N,S chelates have been synthesized, and their electrochemical and absorption data confirmed an electronic effect of introducing the N,S donor. Emission spectra of Ru–polypyridyl complexes with one bidentate N,S chelate coordination recorded at room temperature and 80 K reveal a slight increase in nonradiative decay rates compared with counterpart all-N-coordinated systems.

    17. Fluorescence Quenching

      Fluorescence Quenching in BODIPYs Having Ir- and Rh-Tethered Complexes

      Gong M. Chu, Israel Fernández, Andrés Guerrero-Martínez, Carmen Ramírez de Arellano and Miguel A. Sierra

      Article first published online: 15 JAN 2016 | DOI: 10.1002/ejic.201501283

      Thumbnail image of graphical abstract

      M-BODIPY dyads (M = Rh, Ir) have been prepared by using N-directed C–H activation reactions. The suppression of the BODIPY fluorescence emission in the newly formed dyads by the organometallic moiety occurs by a photoinduced electron transfer (PET) mechanism. The efficiency of the PET depends on the distance between the chromophores in the dyad.

    18. Spin-Crossover Compounds

      Solvent Influence on the Magnetic Properties of Iron(II) Spin-Crossover Coordination Compounds with 4,4′-Dipyridylethyne as Linker

      Katja Dankhoff, Charles Lochenie, Florian Puchtler and Birgit Weber

      Article first published online: 15 JAN 2016 | DOI: 10.1002/ejic.201501175

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      Different solvates of an iron(II) coordination polymer have been prepared. Although the spin-crossover properties of the different solvated forms are different, after removal of the solvent the same three-step spin transition is observed.

    19. Metal β-Thioketoiminates

      Synthesis and Characterization of Methyl–Palladium and –Platinum Complexes Supported by N,O- and N,S-Donor Ligands

      Daniel Ruiz Plaza, José C. Alvarado-Monzón, Gabriel A. Andreu de Riquer, Gerardo González-García, Herbert Höpfl, Luis Manuel de León-Rodríguez and Jorge A. López

      Article first published online: 15 JAN 2016 | DOI: 10.1002/ejic.201501140

      Thumbnail image of graphical abstract

      SacNac ligands [H3CC(S)CHC(NAr)CH3; Ar = Dipp, Mes] react by protonolysis with Me2[Pt] and Me2[Pd] compounds in the presence of PMe3, and AcNac [H3CC(O)CHC(NAr)CH3; Ar = Dipp, Mes] react only with the Me2Pt compounds. The new complexes [ML(CH3)(PMe3)] (L = SacNac, AcNac) are stable under N2. Analyses showed the formation of only one isomer, with the PMe3 co-ligand cis to the S or O atom.

    20. Zinc Coordination Polymers

      Mono-, Di-, and Polymeric Pyridino­ylhydrazone ZnII Complexes: Structure and Photoluminescent Properties

      Fabio Borbone, Ugo Caruso, Simona Concilio, Shiran Nabha, Barbara Panunzi, Stefano Piotto, Rafi Shikler and Angela Tuzi

      Article first published online: 15 JAN 2016 | DOI: 10.1002/ejic.201501132

      Thumbnail image of graphical abstract

      Zinc complexes with pyridinoylhydrazone ligands were obtained from pyridine. Mono-, di-, and polymeric crystalline arrangements were observed, depending on the position of the pyridinoyl nitrogen atom. The meta derivatives led to 1D coordination polymers with unprecedented photoluminescence quantum yields. The discussion was supported by XRD and DFT calculations.

    21. Nitridoborate Nitrides

      Defect-Related Luminescence in ­Nitridoborate Nitride, Mg3Ga(BN2)N2

      Danuta Dutczak, Kai Matthias Wurst, Markus Ströbele, David Enseling, Thomas Jüstel and H.-Jürgen Meyer

      Article first published online: 15 JAN 2016 | DOI: 10.1002/ejic.201501090

      Thumbnail image of graphical abstract

      Nitridoborate nitride Mg3Ga(BN2)N2 was prepared by multilateral solid-state metathesis from MgCl2, GaN, Li3N, and Li3BN2. The crystal structure was refined from X-ray powder diffraction patterns isotypically to Mg3Al(BN2)N2 with the space group Requation imagem no.166 [Z = 3, a = b = 3.4560(0) Å, c = 31.7924(2) Å]. The undoped and Eu2+-doped derivatives show orange-red luminescence under UV excitation.

    22. Hydrogen-Storage Materials

      A Systematic Study on the Prep­aration and Hydrogen Storage of Zeolite 13X-Templated Microporous Carbons

      Zhuxian Yang, Wei Xiong, Jinbo Wang, Yanqiu Zhu and Yongde Xia

      Article first published online: 12 JAN 2016 | DOI: 10.1002/ejic.201501180

      Thumbnail image of graphical abstract

      A systematic study on CVD-based strategies for the nanocasting of porous carbon materials with zeolite 13X as template is presented. The resulting carbon materials exhibit hydrogen-uptake capacities of up to 6.3 wt.-%. Linear relationships between the uptake capacity and the total surface area, the micropore volume, and the micropore surface area were found.

    23. Anode Materials

      SnO2@N-Doped Carbon Hollow Nanoclusters for Advanced Lithium-Ion Battery Anodes

      Lu Li, Lingyu Zhang, Fang Chai, Tingting Wang, Zilu Li, Haiming Xie, Chungang Wang and Zhongmin Su

      Article first published online: 12 JAN 2016 | DOI: 10.1002/ejic.201501307

      Thumbnail image of graphical abstract

      A unique functional nanoarchitecture, SnO2@N-doped carbon hollow nanoclusters, consisting of a large amount of ultrafine small SnO2 nanoparticles, a hollow interior space, and continuous N-doped carbon shells is fabricated. This material shows highly reversible lithium storage and outstanding cycling performance as an anode material for lithium-ion batteries.

    24. Cyanoscorpionate Ligands

      Cyanoscorpionate Ligands: Agostic Interactions in a Series of Metal Complexes Containing the Tris(4-cyano-3-phenylpyrazolyl)borate and Bis(4-cyano-3-phenylpyrazolyl)borate Ligands

      Lava R. Kadel, John R. Bullinger, Robert R. Baum, Curtis E. Moore, David L. Tierney and David M. Eichhorn

      Article first published online: 12 JAN 2016 | DOI: 10.1002/ejic.201501268

      Thumbnail image of graphical abstract

      Less common in scorpionate chemistry are complexes in which one Tp and one Bp ligand are coordinated to the metal. We report five complexes of NiII, MnII, CoII, or FeII involving Tp and Bp ligands comprising either 3-phenyl-4-cyanopyrazole or 3-phenylpyrazole, and a related CoII complex with two Tp ligands. All complexes feature an agostic interaction with a B–H hydrogen atom.

    25. Supports for Fluorescence Quench­ing

      Fluorescence Quenching of Sulfo­rhodamine Dye over Graphene Oxide and Boron Nitride Nanosheets

      Vidhyadevi Thangaraj, Jules Bussiere, Jean-Marc Janot, Mikhael Bechelany, Maguy Jaber, Sivanesan Subramanian, Philippe Miele and Sebastien Balme

      Article first published online: 12 JAN 2016 | DOI: 10.1002/ejic.201501153

      Thumbnail image of graphical abstract

      We report the fluorescence quenching properties of sulforhodamine 640 (SR 640) supported on graphene oxide (GO) and boron nitride (BN) nanosheets (NSs). For GO, the adsorption of dye leads to a non-fluorescent complex, whereas for BN NSs the observed quenching is induced by a decrease in the fluorescence lifetime of the dye.

    26. Mesoporous Silica

      Hybrid Hierarchical Porous Silica Templated in Nanoemulsions for Drug Release

      Philippe Riachy, Ferran Roig, Maria-José García-Celma, Marie-José Stébé, Andrea Pasc, Jordi Esquena, Conxita Solans and Jean Luc Blin

      Article first published online: 12 JAN 2016 | DOI: 10.1002/ejic.201501127

      Thumbnail image of graphical abstract

      A nanocarrier for loading and releasing ketoprofen combines nanoemulsions with mesostructured silica. The release of the drug is pH responsive. By contrast, for the impregnation of ketoprofen in the bare macro-/mesoporous silica, a micelle-assisted release is observed. The modeling of the release profiles with the Korsmeyer–Peppas equation evidences a pseudo-Fickian release mechanism.

    27. Metal–Organic Frameworks

      Cryogenic Nanothermometer Based on the MIL-103(Tb,Eu) Metal–Organic Framework

      Duarte Ananias, Carlos D. S. Brites, Luís D. Carlos and João Rocha

      Article first published online: 5 JAN 2016 | DOI: 10.1002/ejic.201501195

      Thumbnail image of graphical abstract

      Nanoparticles of MIL-103 doped with Tb3+ and Eu3+ are among the best metal–organic framework luminescent (ratiometric) thermometers functioning in the cryogenic range (<100 K), with a relative thermal sensitivity of 2.85 % K–1 at 14 K. Being also microporous, these lanthanide-bearing MIL-103 nanoparticles are, potentially, an excellent multisensing platform.

    28. Fatigue in SCO Materials

      The Spin-Crossover Phenomenon at the Coherent-Domains Scale in 1D Polymeric Powders: Evidence for a Structural Fatigability

      Arnaud Grosjean, Nathalie Daro, Stanislav Pechev, Lucie Moulet, Céline Etrillard, Guillaume Chastanet and Philippe Guionneau

      Article first published online: 30 DEC 2015 | DOI: 10.1002/ejic.201501164

      Thumbnail image of graphical abstract

      The coherent-domain morphology is determined in 1D polymeric spin-crossover iron(II)-based triazole materials. A break in the chains over a large number of thermal spin crossover cycles is demonstrated.

  17. Microreviews

    1. Molecular Machines

      Scorpionate Hydrotris(indazolyl)bor­ate Ligands as Tripodal Platforms for Surface-Mounted Molecular Gears and Motors

      Claire Kammerer and Gwénaël Rapenne

      Article first published online: 23 DEC 2015 | DOI: 10.1002/ejic.201501222

      Thumbnail image of graphical abstract

      This microreview describes the use of scorpionate hydrotris(indazolyl)borate ligands to build structurally rigid bifunctional surface-mounted molecular gears or motors.

  18. Full Papers

    1. Spin Crossover

      Thermal and Light-Induced Spin Transitions of FeII Complexes with 4- and 5-(Phenylazo)-2,2′-bipyridine Ligands: Intra- vs. Intermolecular Effects

      Sven Olaf Schmidt, Holger Naggert, Axel Buchholz, Hannah Brandenburg, Alexander Bannwarth, Winfried Plass and Felix Tuczek

      Article first published online: 23 DEC 2015 | DOI: 10.1002/ejic.201501252

      Thumbnail image of graphical abstract

      Attachment of a phenylazo unit in 4- and 5-position to 2,2′-bipyridine leads to characteristic changes in the spin crossover properties of FeII complexes with bipy ligands

    2. Dual-Mesoporous Silicas

      Hierarchical Meso-Mesoporous and Macro-Mesoporous Silica Templated by Mixtures of Polyoxyethylene ­Fluoroalkyl Ether and Triblock Copolymer

      Anna May-Masnou, Marie José Stébé and Jean Luc Blin

      Article first published online: 23 DEC 2015 | DOI: 10.1002/ejic.201501168

      Thumbnail image of graphical abstract

      Mixtures of polyoxyethylene fluoroalkyl ether and triblock copolymer were used to prepare hierarchical porous silica materials. Dual-mesoporous materials were obtained from the coexistence of two types of micelles through the cooperative templating mechanism (CTM), and macro-mesoporous silica materials were templated by concentrated emulsions.

    3. Nanocomposite Stabilization

      Influence of Reinforcing Nonagglomerated Nanodiamond Particles on Metal Matrix Nanocomposite Structure Stability in the Course of Heat­ing

      Vladimir A. Popov, Evgenij V. Shelekhov and Ekaterina V. Vershinina

      Article first published online: 23 DEC 2015 | DOI: 10.1002/ejic.201501149

      Thumbnail image of graphical abstract

      Aluminium matrix composites with different volume fractions of nonagglomerated nanodiamond reinforcing particles are developed. The uniform distribution of nonagglomerated nano-reinforcements in an aluminium matrix can significantly slow down the recrystallization of the matrix material during heating, which becomes evident only when it is heated above 350 °C.

    4. Photodegradation of Pollutants

      Two Coordination Polymers and Their Silver(I)-Doped Species: Synthesis, Characterization, and High Catalytic Activity for the Photodegradation of Various Organic Pollutants in Water

      Min-Min Chen, Hong-Xi Li and Jian-Ping Lang

      Article first published online: 23 DEC 2015 | DOI: 10.1002/ejic.201501233

      Thumbnail image of graphical abstract

      Two 2D coordination polymers, [M(ppvppa)2(1,3-bdc)]n (M = Cd, Co), have been synthesized by solvothermal reactions. Immersing them into AgNO3 solution produced two AgI-doped polymers, [Cd(ppvppa)2(1,3-bdc)]·AgNO3 and [Co(ppvppa)2(1,3-bdc)]·0.75AgNO3, which showed greatly enhanced catalytic activity towards the photodegradation of various organic pollutants in water compared with their precursors.

  19. Microreviews

    1. Artificial Enzymes

      Solids Go Bio: Inorganic Nanoparticles as Enzyme Mimics

      Ruben Ragg, Muhammad N. Tahir and Wolfgang Tremel

      Article first published online: 23 DEC 2015 | DOI: 10.1002/ejic.201501237

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      This microreview highlights the recent progress in the field of nanoparticles possessing enzyme-like activities, including peroxidase, haloperoxidase, superoxide dismutase and sulfite oxidase mimics. Inorganic nanoparticles are more stable and cost-efficient in synthesis than their natural counterparts, while exhibiting equally high enzymatic activities.

  20. Full Papers

    1. Rare Spin States

      Spectroscopic and Computational Investigation of Low-Spin MnIII Bis(scorpionate) Complexes

      Hannah E. Colmer, Charles G. Margarit, Jeremy M. Smith, Timothy A. Jackson and Joshua Telser

      Article first published online: 23 DEC 2015 | DOI: 10.1002/ejic.201501250

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      Homoleptic MnIII complexes of the scorpionate Tp and Tp* ligands are rare examples of low-spin MnIII species. The electronic structures of these species were compared using MCD spectroscopy and CASSCF/NEVPT2 computations. Complementary computations for the related [{Ph(MeIm)3B}2MnIII]+ species, which features an NHC ligand, explain variations in zero-field splitting for these complexes.

    2. Se-Substituted Phosphaalkenes

      Selenium-Substituted Phosphaalk­enes Obtained through 1,2-Elimination of Chlorosilanes from Selenen­ylchlorophosphines

      Takahiro Sasamori, José Manuel Villalba Franco, Jing-Dong Guo, Koh Sugamata, Shigeru Nagase, Rainer Streubel and Norihiro Tokitoh

      Article first published online: 21 DEC 2015 | DOI: 10.1002/ejic.201500989

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      Stable selenenyl-chlorophosphines, bearing a trisilylalkyl group, were synthesized, and their treatment with Lewis acids such as AlCl3 afforded the corresponding phosphaalkenes. The experimental results and theoretical calculations suggested that the reaction proceeds through the intramolecular 1,2-elimination of chlorosilanes

    3. Spin Crossover Metallomesogens

      Robust Room Temperature Hysteresis in an FeIII Spin Crossover Metallomesogen

      Anthony J. Fitzpatrick, Paulo N. Martinho, Brendan J. Gildea, John D. Holbrey and Grace G. Morgan

      Article first published online: 16 DEC 2015 | DOI: 10.1002/ejic.201501335

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      The high temperature magnetic and structural properties of an amphiphilic iron(III) spin crossover complex are reported. Thermal cycling reveals a scan rate-dependent 20 K thermal hysteresis close to room temperature. Differential scanning calorimetry and cross polarized microscopy are used to show that the magnetic switching aligns with a material change from solid to ordered liquid phase on warming.

    4. Heterophospholes

      Synthesis of 2-Phosphaindolizine and [1,3]Azaphospholo[1,5-a]quin­oline

      Christina Hettstedt, Robert J. Mayer, Jörn F. Martens, Sarah Linert and Konstantin Karaghiosoff

      Article first published online: 15 DEC 2015 | DOI: 10.1002/ejic.201501120

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      A synthetic procedure for preparing 1- and 3-unsubstituted 2-phosphaindolizines has been developed. This new method starts from ClCH2Cl2, PicolylTMS or QuinaldinylTMS and a base to form the desired azaphosphole as the only phosphorus-containing species.

    5. Energy Transfer in Nanocrystals

      Directional Energy Transfer in Nanocrystals of [Ru(2,2′-bipyridine)3]­[NaCr(oxalate)3]

      Elia Previtera, Antoine Tissot and Andreas Hauser

      Article first published online: 14 DEC 2015 | DOI: 10.1002/ejic.201501204

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      The complex sequence of events from the first energy-transfer step in [Ru(bpy)3][NaCr(ox)3] (bpy = 2,2-bipyridine, ox = oxalate) nanocrystals after the initial excitation of [Ru(bpy)3]2+ as sensitizer to [Cr(ox)3]3– in the core of nanocrystals to directional energy migration within the 2E state to the surface chromophores is elucidated.

    6. Silver Deposition

      Silver(I) Bis(pyrazolyl)methane Complexes and Their Implementation as Precursors for Metallic Silver Deposition

      Irene Bassanetti, Monica Mattarozzi, Massimiliano Delferro, Tobin J. Marks and Luciano Marchiò

      Article first published online: 14 DEC 2015 | DOI: 10.1002/ejic.201501236

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      Four new silver complexes with bis(pyrazolyl)methane ligands and two different anions, NO3 and BF4 were investigated to identify suitable candidates as precursors for metallic silver deposition.

  21. Communications

    1. Coordination Polymer Topology

      Framework Isomerism: Highly Augmented Copper(II)-Paddlewheel-­Based MOF with Unusual (3,4)-Net Topology

      Nianyong Zhu, Debobroto Sensharma, Paul Wix, Matthew J. Lennox, Tina Düren, Wai-Yeung Wong and Wolfgang Schmitt

      Article first published online: 14 DEC 2015 | DOI: 10.1002/ejic.201501194

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      An uncommon, less symmetrical, (3,4)-connected net topology that represents a rare framework isomer of the extensively studied {Cu2}-based pto and tbo (platinum oxide or twisted boracite) analogues is reported. Computational analyses suggest that the observed structure gives rise to a surface area that is greater than 3500 m2/g despite the triple-interpenetrated nature of the compound.

    2. Spin Crossover

      The First 1,3,4-Oxadiazole Based Dinuclear Iron(II) Complexes Showing Spin Crossover Behavior with Hysteresis

      Christian Köhler and Eva Rentschler

      Article first published online: 9 DEC 2015 | DOI: 10.1002/ejic.201501278

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      Herein we present a new 1,3,4-oxadiazole bridging ligand and three spin-crossover active dinuclear iron(II) compounds. For two of the complexes a trapped high-spin/low-spin state at temperatures below 170 K was proven. Moreover, the spin state switching could be monitored crystallographically for one complex. The other compound shows a 26 K wide hysteresis in the region of 150–175 K.

  22. Microreviews

    1. Triazaphospholes

      Recent Developments in the Chemistry of 3H-1,2,3,4-Triazaphos­phole Derivatives

      Julian A. W. Sklorz and Christian Müller

      Article first published online: 7 DEC 2015 | DOI: 10.1002/ejic.201500976

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      This microreview provides an overview of recent developments in the chemistry of pyridyl-functionalized 3H-1,2,3,4-triazaphospholes. Access to new chelating, low-coordinate phosphorus heterocycles could lead to a much broader scope for potential applications. New developments in areas such as homogeneous catalysis and phosphorus-containing molecular materials can be foreseen in the near future.

  23. Full Papers

    1. Copper Nanoparticles

      Comparative Synthesis of Cu and Cu2O Nanoparticles from Different Copper Precursors in an Ionic Liquid or Propylene Carbonate

      Raquel Marcos Esteban, Hajo Meyer, Jiyeon Kim, Christian Gemel, Roland A. Fischer and Christoph Janiak

      Article first published online: 7 DEC 2015 | DOI: 10.1002/ejic.201500969

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      Copper metal nanoparticles and copper(I) oxide (cuprite) nanocubes can be easily and reproducibly synthesized under microwave irradiation in an ionic liquid (IL) or propylene carbonate (PC).

  24. Microreviews

    1. Diphosphenes

      Sterically Protected Diphosphenes

      Masaaki Yoshifuji

      Article first published online: 2 DEC 2015 | DOI: 10.1002/ejic.201500990

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      (E)-Bis(2,4,6-tri-tert-butylphenyl)diphosphene was prepared in 1981 for the first time, as a stable compound containing an isolated low-coordinate P=P bond. Since then many sterically protected diphosphenes with various substituents have been prepared, showing remarkable physicochemical features and interesting chemical reactivity.

  25. Full Papers

    1. Hydroxyapatite Thin Films

      Salt-Acid-Surfactant Lyotropic Liquid Crystalline Mesophases: Synthesis of Highly Transparent Mesoporous Calcium Hydroxyapatite Thin Films

      Ebrima Tunkara and Ömer Dag

      Article first published online: 2 DEC 2015 | DOI: 10.1002/ejic.201501116

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      Phosphoric acid and calcium nitrate self-assemble into lyotropic liquid crystalline mesophases that can be calcined into sponge-like transparent mesoporous thin films of calcium hydroxyapatite.

    2. Carbon Dioxide Activation

      Synthesis of Biomimetic Zinc Complexes for CO2 Activation and the Influence of Steric Changes in the Ttz Ligands [Ttz = Tris(triazolyl)borate]

      Sopheavy Siek, Natalie A. Dixon, Mukesh Kumar, Jodi S. Kraus, Kirsten R. Wells, Brittany W. Rowe, Steven P. Kelley, Matthias Zeller, Glenn P. A. Yap and Elizabeth T. Papish

      Article first published online: 30 NOV 2015 | DOI: 10.1002/ejic.201500819

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      New tris(triazolyl)borate (Ttz) complexes of intermediate bulk are useful for forming zinc hydroxide complexes that readily activate carbon dioxide. This study shows that the Ttz ligand's steric and electronic properties influence the outcome of the synthesis and the reactivity. The reaction of (TtziPr2)ZnOH with CO2 was monitored by in situ IR spectroscopy.

    3. Phosphinidene Adducts

      Reactions of Li/Cl Phosphinidenoid Complexes with 1,3,4,5-Tetramethylimidazol-2-ylidene: A New Route to N-Heterocyclic Carbene Adducts of Terminal Phosphin­idene Complexes and an Unprecedented Transformation of an Oxaphosphirane Complex

      Melina Klein, Gregor Schnakenburg, Arturo Espinosa Ferao, Norihiro Tokitoh and Rainer Streubel

      Article first published online: 25 NOV 2015 | DOI: 10.1002/ejic.201500959

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      Reaction of P-Cl phosphinidenoid complexes and an oxaphosphirane complex with an N-heterocyclic carbene (NHC) to give a new zwitterionic phosphaalkene complex is described; the last-named can also be regarded as an NHC adduct of a terminal phosphinidene complex.

    4. Field-Induced SMMs

      Dysprosium- and Ytterbium-Based Complexes Involving Tetrathiafulvalene Derivatives Functionalised with 2,2′-Bipyridine or 2,6-Di(pyrazol-1-yl)-4-pyridine

      Min Feng, Saskia Speed, Fabrice Pointillart, Bertrand Lefeuvre, Boris Le Guennic, Stéphane Golhen, Olivier Cador and Lahcène Ouahab

      Article first published online: 19 NOV 2015 | DOI: 10.1002/ejic.201501145

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      DyIII and YbIII ions adopt spherical tricapped trigonal prism (D3h), spherical capped square antiprism (C4v) and square antiprism (D4d) coordination polyhedra when linked to tetrathiafulvalene-based ligands involving 2,6-di(pyrazol-1-yl)pyridine or 2,2′-bipyridine acceptors. The complex in which the DyIII ion has the most regular C4v symmetry behaves as a field-induced single-molecule magnet.

    5. P–N-Doped Carbon Materials

      Phosphorous–Nitrogen-Codoped Carbon Materials Derived from Metal–Organic Frameworks as Efficient Electrocatalysts for Oxygen Reduction Reactions

      Yu'ang Fu, Yan Huang, Zhonghua Xiang, Guangqing Liu and Dapeng Cao

      Article first published online: 18 NOV 2015 | DOI: 10.1002/ejic.201500822

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      Newly developed P–N carbon materials, derived from modified Uio-66-NH2 by a postsynthetic method, exhibit a high catalytic activity for the oxygen reduction reaction that is close to that of commercial Pt/C catalysts along with superior long-term stability and excellent methanol tolerance.

  26. Short Communications

    1. Phosphinoalumanes

      Synthesis and Structure of Lewis-Base-Free Phosphinoalumane Derivatives

      Tomohiro Agou, Shin Ikeda, Takahiro Sasamori and Norihiro Tokitoh

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejic.201501141

      Thumbnail image of graphical abstract

      Lewis-base-free diphosphinoalumane and 1-hydro-2-chlorophosphinioalumane derivatives bearing a bulky aryl substituent were synthesized from the corresponding lithium phosphide and dichloroalumane. Their structures were determined spectroscopically and by X-ray crystallography. Because of the efficient steric protection by the bulky aryl substituent, their aluminum centers are tricoordinate.

  27. Full Papers

    1. Mesoporous Silica Monoliths

      A Modular Approach towards Meso­porous Silica Monoliths with Organically Modified Pore Walls: Nucleophilic Addition, Olefin Metathesis, and Cycloaddition

      Ronald Göbel, Marcus Stoltenberg, Stefan Krehl, Christine Biolley, Regina Rothe, Bernd Schmidt, Peter Hesemann and Andreas Taubert

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejic.201500638

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      Mesoporous silica monoliths with defined surface chemistry were synthesized by a number of reactions: (i) coupling of an isocyanate to a surface-immobilized thiol, (ii) addition of an epoxide to a surface-immobilized thiol, (iii) cross-metathesis between two olefins, and (iv) Huisgen [2+3] cycloaddition of an alkyne-functionalized silica monolith with an azide.

    2. P–C Cages

      Optically Active P5-Deltacyclenes: A Unique Cage-Inversion Reaction and Some Transition-Metal Complexes of the Rearranged Cage

      Christine Höhn, Walter Bauer, Frank W. Heinemann, Sergi Huguet Torrell, Irene C. Keller, Lars Rohwer, Tatyana E. Shubina and Ulrich Zenneck

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejic.201501015

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      Cage-chiral P–C cage compounds are a new class of chiral ligands. A stereoselective rearrangement performed with highly enriched P5-deltacyclene enantiomers is accompanied by a unique cage inversion, which results in almost mirror-symmetric CD curves of related pairs of P5-deltacyclene/iso-P5-deltacyclene enantiomers. The absolute structure of a W(CO)5 complex enantiomer confirms the observation.

  28. Microreviews

    1. Heterophospholes

      Electron-Rich Aromatic 1,3-Heterophospholes – Recent Syntheses and Impact of High Electron Density at σ2P on the Reactivity

      Joachim W. Heinicke

      Article first published online: 10 NOV 2015 | DOI: 10.1002/ejic.201500941

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      The synthesis, properties, and reactivity of π-excess aromatic σ2P-heterocycles containing the X–C=P–C motif are reviewed. High electron density at σ2P gives these compounds a special position among the σ2P-heterocycles, allowing CH- and NH-lithiation, ambident reactivity of the anions, P-alkylation, catalytic P-arylation, and exclusively μ2- and/or tilted η1-P-coordination in d10 metal complexes.

  29. Short Communications

    1. Photoluminescence

      Synthesis and Photoluminescence Properties of CuI Complexes with Chelating Phosphinito Phosphinine Ligands

      Xiaodan Chen, Zhongshu Li, Fan Yanan and Hansjörg Grützmacher

      Article first published online: 9 NOV 2015 | DOI: 10.1002/ejic.201500933

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      Dinuclear copper(I) halide complexes with a new diphenylphosphinite phosphinine as chelating ligand were prepared. They show tunable phosphorescence in the range 650–700 nm in the solid state at room temperature.

  30. Full Papers

    1. Phosphathioethynolates

      You have full text access to this OnlineOpen article
      Ambient-Temperature Synthesis of 2-Phosphathioethynolate, PCS, and the Ligand Properties of ECX (E = N, P; X = O, S)

      Andrew R. Jupp, Michael B. Geeson, John E. McGrady and Jose M. Goicoechea

      Article first published online: 4 NOV 2015 | DOI: 10.1002/ejic.201501075

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      We report a synthesis of the 2-phosphathioethynolate anion, PCS, under ambient conditions. The coordination chemistry of PCO, PCS and their nitrogen-containing congeners is also explored.

    2. Silylated Phospholes

      A Rational Synthetic Approach to 2,5-Diphenyl-β-silyl Phospholes

      Dieter Klintuch, Kristijan Krekić, Clemens Bruhn, Zoltán Benkő and Rudolf Pietschnig

      Article first published online: 4 NOV 2015 | DOI: 10.1002/ejic.201500874

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      Tuning the fluorescence of phospholes is possible by placing silyl units in the β-position. A general access to these compounds has been opened by modification of a classical procedure.

    3. Luminescent Complexes

      Synthesis and Luminescence Properties of Cycloplatinated Complexes with a Chelating NC Pyridine-Derived N-Heterocyclic Carbene – Influence of 2,4,6-Triphenyl­phosphinine versus Triphenylphosphine

      Jamal Moussa, Gemma R. Freeman, J. A. Gareth Williams, Lise-Marie Chamoreau, Patrick Herson and Hani Amouri

      Article first published online: 30 OCT 2015 | DOI: 10.1002/ejic.201500879

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      Two cycloplatinated complexes with a rare bidentate pyridylpyridylidene NC ligand and triphenylphosphine or 2,4,6-triphenylphosphinine coligands are synthesised and characterised. The phosphinine compound is strongly phosphorescent at 77 K, in contrast to the triphenylphosphine counterpart; this behaviour is probably the result of the exceptional π-acceptor ability of the phosphabenzene ring.


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