European Journal of Inorganic Chemistry

Cover image for Vol. 2015 Issue 7

Special Issue: Hybrid Materials Next Generation (Cluster Issue)

March 2015

Volume 2015, Issue 7

Pages 1084–1308

Issue edited by: Fabrice Leroux, Pierre Rabu, Nico A. J. M. Sommerdijk, Andreas Taubert

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Cover Profile
    5. Editorial
    6. Guest Editorial
    7. Essay
    8. Graphical Abstract
    9. News
    10. Masthead
    11. Microreviews
    12. Full Papers
    1. Furan-Modified Spherosilicates as Building Blocks for Self-Healing Materials (Eur. J. Inorg. Chem. 7/2015)

      Tom Engel and Guido Kickelbick

      Article first published online: 3 MAR 2015 | DOI: 10.1002/ejic.201590027

      Thumbnail image of graphical abstract

      The cover picture shows the molecular building block, which plays the major role in this type of material. The organically functionalized spherosilicate contains furanyl groups at all eight corners, which act as dienes in the Diels–Alder reaction. The synthesis of this inorganic building block is straightforward and it can be achieved easily in a multigram scale. The scheme below shows the principle of the crosslinking and de-crosslinking reaction in the material, which is a prerequisite for the self-healing cycles. In the background, a macroscopic self-healing process is shown by the disappearance of surface scratches, which is also presented in the paper. Details are discussed in the article by T. Engel and G. Kickelbick on p. 1226 ff. For more on the story behind the cover research, see the Cover Profile.

  2. Back Cover

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Cover Profile
    5. Editorial
    6. Guest Editorial
    7. Essay
    8. Graphical Abstract
    9. News
    10. Masthead
    11. Microreviews
    12. Full Papers
    1. Constitutional Hybrid Materials – Toward Selection of Functions (Eur. J. Inorg. Chem. 7/2015)

      Mihail Barboiu

      Article first published online: 3 MAR 2015 | DOI: 10.1002/ejic.201590028

      Thumbnail image of graphical abstract

      The back cover picture shows constitutional hybrid materials composed of columnar silica mesopores used as a scaffolding matrix to orient ribbon-like macrocyclic systems, reversibly connected with the inorganic silica through hydrophobic non-covalent interactions. The dynamic character leads to reversible interactions between the non-grafted organic components and the inorganic hydrophobic silica matrix, making them respond to external ionic stimuli. Evidence has been presented that such systems adapt their internal structure and evolve so as to improve their ion-transport properties. Details are presented in the Microreview by M. Barboiu on p. 1112 ff.

  3. Cover Profile

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Cover Profile
    5. Editorial
    6. Guest Editorial
    7. Essay
    8. Graphical Abstract
    9. News
    10. Masthead
    11. Microreviews
    12. Full Papers
    1. Furan-Modified Spherosilicates as Building Blocks for Self-Healing Materials (page 1084)

      Tom Engel and Guido Kickelbick

      Article first published online: 3 MAR 2015 | DOI: 10.1002/ejic.201500093

      Thumbnail image of graphical abstract

      We wanted to investigate possible routes to incorporate self-healing properties into inorganic?organic hybrid materials...

      Read more about the story behind the cover in the Cover Profile and about the research itself on p. 1226 ff.

  4. Editorial

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Cover Profile
    5. Editorial
    6. Guest Editorial
    7. Essay
    8. Graphical Abstract
    9. News
    10. Masthead
    11. Microreviews
    12. Full Papers
    1. Hybrid Materials

      Hybrid Materials, the Materials for Today's Technology (page 1085)

      Karen J. Hindson

      Article first published online: 3 MAR 2015 | DOI: 10.1002/ejic.201500099

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      Biomimetic ion channels, supported catalysis, metalorganic frameworks, layered double hydroxides and biomineralization are all examples of topics covered in this cluster issue, “Hybrid Materials: Next Generation in Chemistry, Physics and Biology”, presenting a wide variety of inorganic chemistry from synthesis and host–guest chemistry to applications in bioinorganic chemistry, catalysis and fuel cells.

  5. Guest Editorial

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Cover Profile
    5. Editorial
    6. Guest Editorial
    7. Essay
    8. Graphical Abstract
    9. News
    10. Masthead
    11. Microreviews
    12. Full Papers
    1. Hybrid Materials

      Hybrid Materials Engineering in Biology, Chemistry, and Physics (pages 1086–1088)

      Fabrice Leroux, Pierre Rabu, Nico A. J. M. Sommerdijk and Andreas Taubert

      Article first published online: 3 MAR 2015 | DOI: 10.1002/ejic.201500098

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      The Guest Editors emphasize the rapidly growing research in advanced materials. “Telecommunication, health and environment, energy and transportation, and sustainability are just a few examples where new materials have been key for technological advancement.”

  6. Essay

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Cover Profile
    5. Editorial
    6. Guest Editorial
    7. Essay
    8. Graphical Abstract
    9. News
    10. Masthead
    11. Microreviews
    12. Full Papers
    1. Hybrid Materials

      Two-Dimensional Hybrid Materials: Transferring Technology from Biology to Society (pages 1089–1095)

      Fabrice Leroux, Pierre Rabu, Nico A. J. M. Sommerdijk and Andreas Taubert

      Article first published online: 3 MAR 2015 | DOI: 10.1002/ejic.201500153

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      This essay focuses on the specifics and peculiarities of hybrid materials based on two-dimensional (2D) building blocks and confinements. It presents a personal, yet quite broad, account of how hybrid materials, specifically 2D hybrid materials, will provide means to aid modern societies in fields as different as healthcare and energy.

  7. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Cover Profile
    5. Editorial
    6. Guest Editorial
    7. Essay
    8. Graphical Abstract
    9. News
    10. Masthead
    11. Microreviews
    12. Full Papers
    1. Graphical Abstract: Eur. J. Inorg. Chem. 7/2015 (pages 1097–1105)

      Article first published online: 3 MAR 2015 | DOI: 10.1002/ejic.201590024

  8. News

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Cover Profile
    5. Editorial
    6. Guest Editorial
    7. Essay
    8. Graphical Abstract
    9. News
    10. Masthead
    11. Microreviews
    12. Full Papers
  9. Masthead

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Cover Profile
    5. Editorial
    6. Guest Editorial
    7. Essay
    8. Graphical Abstract
    9. News
    10. Masthead
    11. Microreviews
    12. Full Papers
    1. Masthead: Eur. J. Inorg. Chem. 7/2015 (pages 1110–1111)

      Article first published online: 3 MAR 2015 | DOI: 10.1002/ejic.201590026

  10. Microreviews

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Cover Profile
    5. Editorial
    6. Guest Editorial
    7. Essay
    8. Graphical Abstract
    9. News
    10. Masthead
    11. Microreviews
    12. Full Papers
    1. Supramolecular Chemistry

      Constitutional Hybrid Materials – Toward Selection of Functions (pages 1112–1125)

      Mihail Barboiu

      Article first published online: 29 SEP 2014 | DOI: 10.1002/ejic.201402500

      Thumbnail image of graphical abstract

      This review will focus on the implementation of constitutional dynamic chemistry (CDC) toward constitutional hybrid materials, emphasizing recent developments in biomimetic ion channels, membranes, and constitutional hybrid materials.

    2. Host–Guest Chemistry

      Possible Roles of the Spatial Distribution of Organic Guest Species in Mesoporous Silicas to Control the Properties of the Hybrids (pages 1126–1136)

      Makoto Ogawa, Kanji Saito and Minoru Sohmiya

      Article first published online: 12 NOV 2014 | DOI: 10.1002/ejic.201402651

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      The spatial distribution (location, density, and orientation) of the functional units (guest species) attached/included on/in mesoporous silicas are discussed to highlight the status of the host–guest chemistry of mesoporous silicas.

    3. Carbon Materials

      Ionic Liquid Based Approaches to Carbon Materials Synthesis (pages 1137–1147)

      Zai-Lai Xie and Dang Sheng Su

      Article first published online: 14 OCT 2014 | DOI: 10.1002/ejic.201402607

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      Ionic liquids are currently established solvents, precursors for carbon materials, and components of carbon-based ionogels. The unique properties of ionic liquids are beneficial for the formation of unusual carbon materials or composites with homogeneous heteroatom doping (e.g., N, B, S) and controllable porosity.

    4. Ionogels

      Electrospinning of Ionogels: Current Status and Future Perspectives (pages 1148–1159)

      Andreas Taubert

      Article first published online: 25 NOV 2014 | DOI: 10.1002/ejic.201402490

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      Spin it: Electrospinning is a useful and low-cost approach towards high-surface-area nanofibrous ionogels, that is, multifunctional hybrid materials based on ionic liquids, with tremendous application potential from catalysis to energy, healthcare, and beyond. The article provides an overview of the field and discusses the future potential of these promising materials.

  11. Full Papers

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Cover Profile
    5. Editorial
    6. Guest Editorial
    7. Essay
    8. Graphical Abstract
    9. News
    10. Masthead
    11. Microreviews
    12. Full Papers
    1. Nickel Nanoparticles

      A Neutral 1D Coordination Polymer Constructed from the NiII Complex of the N-Phosphorylated Thiourea PhNHC(S)NHP(O)(OPh)2 and Pyrazine: A Single-Source Precursor for Nickel Nanoparticles (pages 1160–1166)

      Maria G. Babashkina, Damir A. Safin, Koen Robeyns and Yann Garcia

      Article first published online: 3 JUN 2014 | DOI: 10.1002/ejic.201402278

      Thumbnail image of graphical abstract

      Interaction of [Ni{PhNHC(S)NP(O)(OPh)2}2] with pyrazine (pz) yielded the 1:1 coordination polymer [NiL2pz]n, in which the coordination mode of L changed unexpectedly from 1,3-N,S- to 1,5-O,S-[NiL2pz]n dissolved in tri-n-octylphosphine (TOP) is decomposed in hot hexadecylamine to give TOP-capped face-centered cubic Ni nanoparticles with an average particle size of 17(2) nm.

    2. Selective Crystallization

      Sulfonated Polymethylsiloxane as an Additive for Selective Calcium Oxalate Crystallization (pages 1167–1177)

      Andrónico Neira-Carrillo, Fabian Luengo-Ponce, Patricio Vásquez-Quitral, Mehrdad Yazdani-Pedram, María Soledad Fernández, Helmut Cölfen and José Luis Arias

      Article first published online: 27 JUN 2014 | DOI: 10.1002/ejic.201402063

      Thumbnail image of graphical abstract

      Sulfonated and fluorescent polymethylsiloxanes (SO3H-PMS) were synthesized and used as additives for in vitro calcium oxalate (CaOx) crystallization. The strong modifying capacity of SO3HPMS on CaOx morphologies and CaOx monohydrate (COM) and CaOx dihydrate (COD) crystal types was demonstrated. Fluorescent CaOx crystals were also produced by the inclusion of SO3H-PMS into the CaOx matrix.

    3. Crystal Nucleation

      Molecular Mechanisms of [Bi6O4(OH)4](NO3)6 Precursor Activation, Agglomeration, and Ripening towards Bismuth Oxide Nuclei (pages 1178–1181)

      Markus Walther and Dirk Zahn

      Article first published online: 13 NOV 2014 | DOI: 10.1002/ejic.201402751

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      Molecular dynamics simulations unravel the early steps of bismuth oxide precursor association and ripening into larger aggregates. Nitrate ions play a twofold role in the process by preventing the association of Bi6O4(OH)4(NO3)6 clusters but at the same time inducing the formation of oligomers comprising under-coordinated Bi ions.

    4. Coordination Polymers

      Coordination Polymers Based on Alkylboronate Ligands: Synthesis, Characterization, and Computational Modelling (pages 1182–1191)

      Dorothée Berthomieu, Christel Gervais, Guillaume Renaudin, Marc Reinholdt, Saad Sene, Mark E. Smith, Christian Bonhomme and Danielle Laurencin

      Article first published online: 9 SEP 2014 | DOI: 10.1002/ejic.201402561

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      The synthesis and characterization of three new crystalline alkylboronate structures are described, together with their DFT modelling and calculations of solid-state NMR parameters and IR O–H stretching frequencies.

    5. Nanocomposite Films

      Preparation of Alginate/Graphene Oxide Hybrid Films and Their Integration in Triboelectric Generators (pages 1192–1197)

      Luca Valentini, Nicoletta Rescignano, Debora Puglia, Marta Cardinali and Josè Kenny

      Article first published online: 6 OCT 2014 | DOI: 10.1002/ejic.201402610

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      Sodium alginate/graphene oxide nanocomposite films were prepared by a solvent-casting method. We report the proof of concept that such a hybrid system can be used as the active component of a triboelectric generator. The involvement of a biodegradable polymer might introduce new applications in biodegradable/biocompatible electronics.

    6. Gas Adsorbing Materials

      Efficient Hybrid-Type CO2 Adsorbents of Reassembled Layered Double Hydroxide 2D Nanosheets with Polyoxometalate 0D Nanoclusters (pages 1198–1202)

      Jayavant L. Gunjakar, In Young Kim and Seong-Ju Hwang

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402480

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      Porous nanohybrids of Mg-Al-layered double hydroxide (LDH) 2D nanosheets and polyoxometalate 0D nanoclusters are synthesized by an exfoliation–reassembling process. The resulting nanohybrid materials show promising CO2 adsorption capabilities exceeding those of pristine Mg-Al-LDH, underscoring the usefulness of the present hybridization method in optimizing gas adsorption by LDH materials.

    7. Polyurethane Nanocomposites

      Synthesis of Advanced Nanoreinforced Polyurethane with Thiolene Photografted Organo-Modified Layered Double Hydroxide (pages 1203–1211)

      Audrey Ramoné, Audrey Diouf-Lewis, Florence Delor-Jestin, Rémi Auvergne, Sylvain Caillol, Vincent Verney and Fabrice Leroux

      Article first published online: 12 NOV 2014 | DOI: 10.1002/ejic.201402602

      Thumbnail image of graphical abstract

      Successive processes to yield layered double hydroxide filled polyurethane nanocomposite including (1) organo-modification of LDH platelets, (2) functionalization using UV thiolene coupling and (3) monomer addition.

    8. Composite Structures

      Optical and Electrooptical Properties of Porous-Silicon/Conjugated-Polymer Composite Structures (pages 1212–1217)

      Amit Nahor, Itai Shalev, Amir Sa'ar and Shlomo Yitzchaik

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402450

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      An organic–inorganic hybrid structure consisting of porous silicon and nanowires of poly(N-vinylcarbazole) (PVK) exhibits optical behavior of the PVK nanowires, which is unique when compared with the bulk material. Furthermore, a simple method to control the band alignment between type-I and type-II is demonstrated. Our results enable a variety of applications and electrooptical characteristics.

    9. Layered Compounds

      Nanostructuring of Bridged Organosilane Precursors with Pendant Alkyl Chains (pages 1218–1225)

      Sílvia C. Nunes, Kristýna Bürglová, Jana Hodačová, Rute A. S. Ferreira, Luís D. Carlos, Paulo Almeida, Xavier Cattoën, Michel Wong Chi Man and Verónica de Zea Bermudez

      Article first published online: 1 OCT 2014 | DOI: 10.1002/ejic.201402673

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      A new bridged silsesquioxane with hierarchically structured lamellar bilayer structure and a texture composed of microplates of nanometer thickness was obtained by sol-gel and self-assembly by using a bridged organosilane carrying a pendant icosanyl chain produced by click chemistry. The hybrid exhibits a time-independent reversible order/disorder phase transition in a heating-cooling cycle.

    10. Self-Healing Materials

      Furan-Modified Spherosilicates as Building Blocks for Self-Healing Materials (pages 1226–1232)

      Tom Engel and Guido Kickelbick

      Article first published online: 9 SEP 2014 | DOI: 10.1002/ejic.201402551

      Thumbnail image of graphical abstract

      Octameric furfuryl-functionalized spherosilicates were used to prepare self-healing hybrid materials based on a reversible Diels–Alder reaction. Two different bismaleimides were used as dienophilic cross-linkers for the self-healing materials. The healing abilities are dictated by the nature of the cross-linker.

    11. Two-Photon Absorption

      Two-Photon Absorption Properties of Eu3+-DPA-Triazolyl Complexes and the Derived Silica Nanoparticles Embedding These Complexes (pages 1233–1242)

      Pierre Adumeau, Claire Gaillard, Damien Boyer, Jean-Louis Canet, Arnaud Gautier and Rachid Mahiou

      Article first published online: 21 NOV 2014 | DOI: 10.1002/ejic.201402617

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      The TRS technique is used at 300 K to analyze the phosphorescence and the NIR excitation spectra of Gd3+-, Eu3+-DPA-triazolyl complexes and derived NPs embedding them. The TPA excitation spectra of the NPs are located on the low-energy side of the phosphorescence spectrum and consist of narrow bands attributed to the S0(0)[RIGHTWARDS ARROW]T1(0–2) pure electronic transition.

    12. Imaging Agents

      Glycine–Nitrate Process for the Elaboration of Eu3+-Doped Gd2O3 Bimodal Nanoparticles for Biomedical Applications (pages 1243–1253)

      Graziella Goglio, Gaganpreet Kaur, Sonia L. C. Pinho, Nicolas Penin, Alexia Blandino, Carlos F. G. C. Geraldes, Alain Garcia and Marie-Helene Delville

      Article first published online: 18 NOV 2014 | DOI: 10.1002/ejic.201402721

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      By fine control of the flame temperature in the glycine–nitrate process, highly crystalline Eu3+-doped and undoped Gd2O3 nanoparticles are obtained. In the doped samples, the Eu3+ ions are homogeneously distributed over the whole material. The Eu:Gd2O3 NPs are highly luminescent and exhibit relaxivities that define them as potential T1 contrast agents for biomedical applications.

    13. Luminescence

      Modelling the Luminescence of Phosphonate Lanthanide–Organic Frameworks (pages 1254–1260)

      Mariela M. Nolasco, Ricardo F. Mendes, Patrícia P. Lima, Filipe A. Almeida Paz, Luís D. Carlos and João Rocha

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402492

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      The applicability of the LUMPAC software for calculations of the photoluminescence properties of metal–organic frameworks is assessed by considering three systems with a ditopic 1,4-phenylenebis(methylene)diphosphonic acid ligand and Eu3+ ions. A simple method based on the crystallographic structural subunits affords excellent agreement between the calculated and experimental photoluminescence.

    14. Surface Functionalization

      Spatially Confined Functionalization of Transparent NiO Thin Films with a Luminescent (1,10-Phenanthroline)tris(2-thenoyltrifluoroacetonato)europium Monolayer (pages 1261–1268)

      Emanuele Smecca, Cristina Tudisco, Antonino E. Giuffrida, Maria R. Catalano, Adolfo Speghini, Graziella Malandrino and Guglielmo G. Condorelli

      Article first published online: 12 SEP 2014 | DOI: 10.1002/ejic.201402479

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      Anchoring of the Eu(TTA)3phen complex on MOCVD-grown NiO films is reported. The NiO surface was activated by means of a sputtering process and functionalized with a phosphonic linker, followed by the coordination of the Eu complex through a ligand-exchange reaction. The luminescent hybrid system has been proven to retain the optical properties of the Eu complex.

    15. Polymorphs

      Prospective Electroluminescent Hybrid Materials (pages 1269–1274)

      Olga B. Petrova, Roman I. Avetisov, Andew V. Khomyakov, Rasim R. Saifutyarov, Alina A. Akkuzina, Elena N. Mozhevitina, Alexandr V. Zhukov and Igor Ch. Avetissov

      Article first published online: 12 SEP 2014 | DOI: 10.1002/ejic.201402538

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      Three polymorphs of tris(8-hydroxyquinoline)boron (Bq3) were obtained by high-temperature substitution reaction. Their spectral and structural properties were investigated and showed Bq3 to be a potential blue emitter. Hybrid material (HM) films B2O3/Alq3/B2O3 on a glass substrate were made by vacuum sputtering. Laser heating of the HM film resulted in an irreversible change in its photoluminescence.

    16. Biosensing

      Properties of an Indium Tin Oxide Electrode Modified by a Laser Nanostructured Thin Au Film for Biosensing (pages 1275–1281)

      Katarzyna Grochowska, Katarzyna Siuzdak and Gerard Śliwiński

      Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402485

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      Thin Au films on ITO that were stepwise patterned by means of nanosecond UV laser pulses transformed into semi-regular nanoparticle arrays. The modified electrode showed enhanced activity towards ferricyanide redox systems as well as glucose, and can be considered for the production of a non-enzymatic biosensor.

    17. Ionic Liquids

      Organic–Inorganic Hybrid Membranes Based on Sulfonated Poly(ether ether ketone) and Tetrabutylphosphonium Bromide Ionic Liquid for PEM Fuel Cell Applications (pages 1282–1289)

      Vijay Shankar Rangasamy, Savitha Thayumanasundaram, Niels de Greef, Jin Won Seo and Jean-Pierre Locquet

      Article first published online: 19 SEP 2014 | DOI: 10.1002/ejic.201402558

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      Polymer–ionic liquid electrolyte membranes were fabricated from tetrabutylphosphonium bromide ([P4 4 4 4]Br) and sulfonated poly(ether ether ketone) (SPEEK). Their thermal, mechanical, structural and electrical properties show promise for their use in high-temperature fuel cell applications.

    18. Electrolytes

      Hybrid Polymer Electrolytes Based on a Poly(vinyl alcohol)/Poly(acrylic acid) Blend and a Pyrrolidinium-Based Ionic Liquid for Lithium-Ion Batteries (pages 1290–1299)

      Savitha Thayumanasundaram, Vijay Shankar Rangasamy, Niels De Greef, Jin Won Seo and Jean-Pierre Locquet

      Article first published online: 11 NOV 2014 | DOI: 10.1002/ejic.201402603

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      Mechanically stable polymer membranes for lithium-ion batteries consist of 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (PYR14TFSI) doped with 0.2 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).

    19. Conformation Studies

      Conformational Changes and Phase Behaviour in the Protic Ionic Liquid 1-Ethylimidazolium Bis(trifluoromethylsulfonyl)imide in the Bulk and Nano-Confined State (pages 1300–1308)

      Anna Martinelli

      Article first published online: 29 SEP 2014 | DOI: 10.1002/ejic.201402496

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      Conformational changes of the TFSI anion in the protic ionic liquid C2HImTFSI have been monitored by temperature-dependent Raman spectroscopy for the bulk and nano-confined states. Phase behaviours have also been spectroscopically investigated at a range of temperatures. In the nano-confined state the cis form predominates and the enthalpic term was higher.

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