Macromolecular Rapid Communications

Cover image for Vol. 33 Issue 6‐7

Special Issue: Macromolecules Containing Metal Ions

April 13, 2012

Volume 33, Issue 6-7

Pages 437–615

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Masthead
    5. Contents
    6. Editorial
    7. Feature Articles
    8. Communications
    1. Macromol. Rapid Commun. 6-7/2012 (page 437)

      Christian Friebe, Andreas Wild, Jolke Perelaer and Ulrich S. Schubert

      Article first published online: 5 APR 2012 | DOI: 10.1002/marc.201290021

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      Front Cover: For the first time, thin-film libraries of zinc(II) bis-2,2′:6′,2″-terpyridine metallopolymers are prepared by inkjet printing to study structure–property relationships and their possible usage for organic photovoltaic (OPV) or polymer light-emitting diode (PLED) applications. Using a combinatorial approach, various important parameters, including solvent system, dot spacing, and substrate temperature, as well as UV–vis absorption and emission properties, can be screened in a materials-efficient and reproducible manner. Further details can be found in the article by C. Friebe, A. Wild, J. Perelaer, and U. S. Schubert* on page 503.

  2. Back Cover

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Masthead
    5. Contents
    6. Editorial
    7. Feature Articles
    8. Communications
    1. Macromol. Rapid Commun. 6-7/2012 (page 620)

      Katy A. Green, Peter V. Simpson, T. Christopher Corkery, Marie P. Cifuentes, Marek Samoc and Mark G. Humphrey

      Article first published online: 5 APR 2012 | DOI: 10.1002/marc.201290022

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      Front Cover: Two-photon absorption (TPA) is of interest for optical power limiting, data storage, two-photon microscopy, microfabrication, frequency up-conversion lasing, and many other applications. Highly efficient inorganic TPA molecules are now reported. Ruthenium alkynyl den-drimers up to second generation in size have been prepared by a divergent route and exploiting Sonogashira coupling. These compounds display an NLO dendrimer effect – their cubic nonlinearities and two-photon absorption cross-sections increase nonlinearly on increasing dendrimer generation. Further details can be found in the article by K. A. Green, P. V. Simpson, T. C. Corkery, M. P. Cifuentes, M. Samoc, and M. G. Humphrey* on page 573.

  3. Masthead

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Masthead
    5. Contents
    6. Editorial
    7. Feature Articles
    8. Communications
    1. Macromol. Rapid Commun. 6-7/2012

      Article first published online: 5 APR 2012 | DOI: 10.1002/marc.201290023

  4. Contents

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Masthead
    5. Contents
    6. Editorial
    7. Feature Articles
    8. Communications
    1. Macromol. Rapid Commun. 6-7/2012 (pages 439–445)

      Article first published online: 5 APR 2012 | DOI: 10.1002/marc.201290020

  5. Editorial

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Masthead
    5. Contents
    6. Editorial
    7. Feature Articles
    8. Communications
    1. Macromolecules Containing Metal Ions (page 447)

      George. R. Newkome, Ian. Manners, Stephanie Schubert and Ulrich. S. Schubert

      Article first published online: 5 APR 2012 | DOI: 10.1002/marc.201200088

  6. Feature Articles

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Masthead
    5. Contents
    6. Editorial
    7. Feature Articles
    8. Communications
    1. Polystannanes: Synthesis, Properties, and Outlook (pages 448–460)

      Markus Trummer, Fabien Choffat, Paul Smith and Walter Caseri

      Article first published online: 22 MAR 2012 | DOI: 10.1002/marc.201100794

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      Polystannanes are a unique type of polymer and their main chain is composed of covalently bound metal atoms. Polystannanes have attracted much interest in polymer science. Information on various aspects of these polymers, including their synthesis, properties, processing, orientation, degradation, and stabilization is provided.

    2. New Trends in the Optical and Electronic Applications of Polymers Containing Transition-Metal Complexes (pages 461–480)

      Shu-Juan Liu, Yang Chen, Wen-Juan Xu, Qiang Zhao and Wei Huang

      Article first published online: 5 MAR 2012 | DOI: 10.1002/marc.201100775

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      Polymers containing transition-metal complexes, one of the most excellent optoelectronic materials, have attracted more and more research interest in recent years. They exhibit excellent optoelectronic properties, combining the advantages of both polymers and metal complexes. New research trends in the optical and electronic applications of polymers containing transition-metal complexes are summarized.

    3. Light-Induced Dynamics in Conjugated Bis(terpyridine) Ligands – A Case Study Toward Photoactive Coordination Polymers (pages 481–497)

      Ronald Siebert, Andreas Winter, Michael Schmitt, Jürgen Popp, Ulrich S. Schubert and Benjamin Dietzek

      Article first published online: 16 MAR 2012 | DOI: 10.1002/marc.201100753

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      Investigation of photoinduced dynamics in terpyridine systems presents a cornerstone in the guided design toward innovative photoactive materials. This contribution features recent work dissecting the complex photoinduced processes in terpyridine-based coordination complexes and polymers into dynamics associated with the individual molecular building blocks.

  7. Communications

    1. Top of page
    2. Cover Picture
    3. Back Cover
    4. Masthead
    5. Contents
    6. Editorial
    7. Feature Articles
    8. Communications
    1. Low-Power Upconversion in Dye-Doped Polymer Nanoparticles (pages 498–502)

      Yoan C. Simon, Shuo Bai, Michelle K. Sing, Hervé Dietsch, Marc Achermann and Christoph Weder

      Article first published online: 3 FEB 2012 | DOI: 10.1002/marc.201100708

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      The fabrication of dye-doped cross-linked rubbery nanoparticles that exhibit upconversion even at relatively low power densities is reported here. Successful loading of an upconverting dye pair into the nanoparticles following surfactant-free emulsion polymerization is reported. In addition to optical properties, the nanoparticles were characterized by electron microscopy and dynamic light scattering.

    2. Inkjet Printing of Zinc(II) Bis-2,2′:6′,2″-Terpyridine Metallopolymers: Printability and Film-Forming Studies by a Combinatorial Thin-Film Library Approach (pages 503–509)

      Christian Friebe, Andreas Wild, Jolke Perelaer and Ulrich S. Schubert

      Article first published online: 31 JAN 2012 | DOI: 10.1002/marc.201100713

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      Thin-film libraries of zinc(II) bis-2,2′:6′,2″- terpyridine metallopolymers were prepared by inkjet printing to study structure–property relationships between the synthesized polymers and their possible usage for organic photovoltaic (OPV) or polymer light-emitting diode (PLED) applications. Several processing parameters, including dot spacing, solvent system, substrate temperature, and UV-vis absorption/emission, were studied, for the first time, in a combinatorial approach using inkjet printing.

    3. Cobaltocenium-Containing Block Copolymers: Ring-Opening Metathesis Polymerization, Self-Assembly and Precursors for Template Synthesis of Inorganic Nanoparticles (pages 510–516)

      Lixia Ren, Jiuyang Zhang, Christopher G. Hardy, Shuguo Ma and Chuanbing Tang

      Article first published online: 18 JAN 2012 | DOI: 10.1002/marc.201100732

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      Cationic cobaltocenium-containing block copolymers are prepared by ring-opening metathesis polymerization. These block copolymers exhibit counterion-dependent self-assembly in solutions. The stability of the self-assembled micelles is dictated by ion exchange between the two different segments. These micelles are further used as templates to prepare oxidized cobalt nanoparticles, which show a magnetic response.

    4. Perfluorophenyl-Terpyridine Ruthenium Complex as Monomer for Fast, Efficient, and Mild Metallopolymerizations (pages 517–521)

      Andreas Wild, Andreas Winter, Martin D. Hager, Helmar Görls and Ulrich S. Schubert

      Article first published online: 27 JAN 2012 | DOI: 10.1002/marc.201100711

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      A new, fast, and efficient method for the synthesis of ruthenium(II) bis terpyridine metallopolymers is presented. The homoleptic RuII complex of 4′-(perfluorophenyl)-2,2′:6′,2″-terpyridine is a versatile monomer for a thiol -para- fluorine click reaction and can easily be converted with π-conjugated dithiols resulting in metallopolymers in a fast and efficient manner.

    5. Photonics of a Conjugated Organometallic Pt–Ir Polymer and Its Model Compounds Exhibiting Hybrid CT Excited States (pages 522–527)

      Ahmed M. Soliman, Daniel Fortin, Eli Zysman-Colman and Pierre D. Harvey

      Article first published online: 17 JAN 2012 | DOI: 10.1002/marc.201100721

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      An innovative polymer built upon charged iridium(III), [Ir], and neutral platinum(II) units, [Pt], exhibiting charge transfer excited states [Pt][RIGHTWARDS ARROW][Ir], has been prepared. The absorption and emission spectra exhibit features reminiscent of both chromophores, and the emission lifetimes and quantum yields are intermediate between those for the isolated units, indicating a unique case of formation of hybrid excited states.

    6. Synthesis of Main-Chain Metallo-Copolymers Containing Donor and Acceptor Bis-Terpyridyl Ligands for Photovoltaic Applications (pages 528–533)

      Harihara Padhy, Mohan Ramesh, Dhananjaya Patra, Rudrakanta Satapathy, Murali Krishna Pola, Hsuan-Chih Chu, Chih-Wei Chu, Kung-Hwa Wei and Hong-Cheu Lin

      Article first published online: 9 JAN 2012 | DOI: 10.1002/marc.201100752

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      ZnII and RuII metallo-copolymers composed of donor- and acceptor-substituted bis-terpyridyl ligands were synthesized and their electo-optical properties were investigated. Compared with the other conjugated polyelectrolytes, the PVC device with a configuration of ITO/PEDOT:PSS/P4:PC61BM (1:1, w/w)/Ca/Al yielded the highest PCE value of 0.90% with Voc = 0.70 V, Jsc = 3.50 mA cm−2, and FF = 0.37.

    7. Temperature-Responsive Aqueous Micelles From Terpyridine End-Capped Poly(N-Isopropylacrylamide)-Block-Polystyrene Diblock Copolymers (pages 534–539)

      Sandie Piogé, Charles-André Fustin and Jean-François Gohy

      Article first published online: 21 DEC 2011 | DOI: 10.1002/marc.201100640

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      Aqueous micelles have been prepared from poly(N-isopropylacrylamide)-block-polystyrene copolymers functionalized at the extremity of their poly(N-isopropylacrylamide) coronal chains by terpyridine ligands. The effect of temperature and of the addition of Zn(II) ions on those micelles has been then studied.

    8. Facile Preparation of a Fully π-Conjugated Metallopolymer Composed of Fused Salphen Complexes (pages 540–544)

      Keisuke Yagi, Muneyuki Ito and Hirohiko Houjou

      Article first published online: 30 JAN 2012 | DOI: 10.1002/marc.201100766

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      A macromolecule composed of an indefinite number of Zn-salphen complexes fused into a unique conjugated system is synthesized. The repeating molecular structure is spectroscopically examined by comparison with its analogous oligomers, including a newly synthesized tetranuclear complex. The XRD pattern suggests that the molecular assembly is highly ordered in the solid state by virtue of various intermolecular interactions.

    9. Transformation of Regioregular Organotitanium Polymers into Group 16 Heterole-Containing π-Conjugated Materials (pages 545–549)

      Hiroki Nishiyama, Tomoko Kino and Ikuyoshi Tomita

      Article first published online: 2 FEB 2012 | DOI: 10.1002/marc.201100751

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      Reactions of regioregular organometallic polymers possessing titanacyclopentadiene-2,5-diyl units to give polymers containing thiophene or selenophene units are described. The transformation of the main chain structure of the organotitanium polymer takes place smoothly by reactions with S2Cl2 or Se2Cl2 to give fully π-conjugated polymers with high HOMO energy levels.

    10. Synthesis of π-Conjugated Polymers Containing Aminoquinoline-Borafluorene Complexes in the Main-Chain (pages 550–555)

      Yuichiro Tokoro, Atsushi Nagai, Kazuo Tanaka and Yoshiki Chujo

      Article first published online: 27 JAN 2012 | DOI: 10.1002/marc.201100773

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      An aminoquinoline-borafluorene complex is successfully incorporated into a main-chain of poly(arylene-ethynylene)s. This moiety restricts two aromatic planes, aminoquinoline and borafluorene, orthogonally, and extends the π-conjugation of the main-chain. The aminoquinolate moiety acts as a moderate electron acceptor so that the side-chains of the polymers regulate the fluorescence quantum yields by electron transfer.

    11. Metallo-Supramolecular Materials Based on Amine-Grafting Onto Polypentafluorostyrene (pages 556–561)

      Christina Ott, Christoph Ulbricht, Richard Hoogenboom and Ulrich S. Schubert

      Article first published online: 30 JAN 2012 | DOI: 10.1002/marc.201100769

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      The post-modification reaction of poly(pentafluorostyrene) allows the effective grafting of supramolecular binding motifs onto the linear polymer backbone. A metallo-supramolecular gel was obtained after the addition of iron ions as well as a phoshorescent iridium-containing polymer by grafting amine-functionalized metal complexes to the polymer.

    12. Self-Assembly of Borane End-Functionalized Polystyrene Through Tris(1-pyrazolyl)borate (Tp) Iron(II) Linkages (pages 562–567)

      Yang Qin, Patrick O. Shipman and Frieder Jäkle

      Article first published online: 8 FEB 2012 | DOI: 10.1002/marc.201100628

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      Commonly referred to as “scorpionates”, poly(1-pyrazolyl)borate (Tp) ligands possess powerful coordination chemistry toward transition metals. In this paper, we introduce a new class of telechelic polymers that are functionalized with Tp ligands and explore their self-assembly into supramolecular structures via coordination to Fe(II). Successful formation of supramolecular polymers was confirmed through NMR, GPC, DSC, CV, and UV–vis analyses.

    13. Luminescent and Light Refractive Polymers: Synthesis and Optical and Photonic Properties of Poly(arylene ethynylene)s Carrying Silole and Tetraphenylethene Luminogenic Units (pages 568–572)

      Cathy K. W. Jim, Jacky W. Y. Lam, Anjun Qin, Zujin Zhao, Jianzhao Liu, Yuning Hong and Ben Zhong Tang

      Article first published online: 1 FEB 2012 | DOI: 10.1002/marc.201100768

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      Soluble, high molecular weight poly(arylene ethynylene)s are constructed in high yields from silole and tetraphenylethene building blocks. The polymers are thermally stable and light emissive. They exhibit high refractive indices and can generate negative photoresist patterns upon UV irradiation.

    14. Divergent Synthesis of Ruthenium Alkynyl Dendrimers and a Two-Photon Absorption Cross-Section Dendritic Effect (pages 573–578)

      Katy A. Green, Peter V. Simpson, T. Christopher Corkery, Marie P. Cifuentes, Marek Samoc and Mark G. Humphrey

      Article first published online: 1 FEB 2012 | DOI: 10.1002/marc.201100770

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      Ruthenium alkynyl dendrimers incorporating 1,2-bis(diphenylphosphino)ethane co-ligands have been synthesized in a divergent manner, utilizing Pd-catalyzed coupling at organometallic fragments. These compounds display an NLO dendrimer effect – their cubic nonlinearities and two-photon absorption cross-sections increase nonlinearly on increasing dendrimer generation.

    15. Poly(ϵ-caprolactone) Decorated With One Room-Temperature Red-Emitting Ruthenium(II) Complex: Synthesis, Characterization, Thermal and Optical Properties (pages 579–584)

      Marcus Schulze, Michael Jäger and Ulrich S. Schubert

      Article first published online: 31 JAN 2012 | DOI: 10.1002/marc.201100783

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      An efficient assembly strategy of light-active complexes into polymers is essential for future energy conversion materials. The scope of positional control of suitable metal complexes is investigated by functional initiators and post-modification of poly(ϵ-caprolactone). The prepared dye-labeled polymers display blue or red emission at ambient conditions.

    16. Heteroleptic Ruthenium(II) Complex-Containing Polymers and Their Bandgap Tuning and Photosensitizing Properties (pages 585–591)

      Wai Kei Cheung, Chris S. K. Mak and Wai Kin Chan

      Article first published online: 8 FEB 2012 | DOI: 10.1002/marc.201100756

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      Conjugated polymers incorporated with heteroleptic ruthenium complexes were synthesized by palladium-catalyzed reaction. The electronic absorption of the polymer main chain was strongly dependent on the ligand on the metal center, which showed a significant red shift compared with the metal-free polymers. The potentials of using these polymers for photosensitizers in organic photovoltaic devices were demonstrated.

    17. Functionalization of Poly(ferrocenyldimethylsilane) via Lithiation of the Cyclopentadienyl Rings (pages 592–596)

      Alejandro Presa Soto, Laurent Chabanne, Jiawen Zhou, Joe B. Gilroy and Ian Manners

      Article first published online: 13 MAR 2012 | DOI: 10.1002/marc.201100811

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      The reaction between poly(ferrocenyldimethylsilane) (PFDMS) and Schlosser's base (t-BuLi/KOt-Bu pair) in THF at low temperature results in the lithiation of the Cp rings. Further reaction with trimethylsilyl chloride or D2O afforded Cp-substituted PFDMSs with up to 1.8 new substituents per repeating unit. NMR spectroscopic analyses of these products suggest regioselective lithiation at the β position of the Cp ligands.

    18. Ruthenium(II) Metallo-Supramolecular Polymers of Click-Derived Tridentate Ditopic Ligands (pages 597–602)

      Benjamin Schulze, Christian Friebe, Stephanie Hoeppener, Georges M. Pavlov, Andreas Winter, Martin D. Hager and Ulrich S. Schubert

      Article first published online: 19 MAR 2012 | DOI: 10.1002/marc.201100782

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      Linear-rigid ruthenium(II) metallo-supramolecular polymers featuring a π-conjugated spacer and tridentate ligands with clicked-on solubilizing groups were synthesized and studied by size exclusion chromatography and analytical ultracentrifugation as well as atomic force and transmission electron microscopy revealing a photoredoxactive polymer that allows for the preparation of solution-processed films.

    19. Platinum-Based Poly(Aryleneethynylene) Polymers Containing Thiazolothiazole Group with High Hole Mobilities for Field-Effect Transistor Applications (pages 603–609)

      Lei Yan, Yan Zhao, Xiaohui Wang, Xing-Zhu Wang, Wai-Yeung Wong, Yunqi Liu, Weiping Wu, Qingzhen Xiao, Guo Wang, Xuan Zhou, Wei Zeng, Chengxi Li, Xiaoyu Wang and Hongbin Wu

      Article first published online: 28 MAR 2012 | DOI: 10.1002/marc.201200018

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      Two platinum-acetylide polymers functionalized with the electron-deficient thiazolothiazole spacer are synthesized that exhibit p-channel field-effect charge transport characteristics with an impressive peak field-effect charge-carrier mobility of (2.1–2.8) × 10−2 cm2 V−1 s−1 and an on/off ratio of (0.8–1.0) × 105 for the holes. The high hole mobility value is among the highest reported for metallopolyynes to date.

    20. Conducting Metallopolymers as Precursors to Fabricate Palladium Nanoparticle/Polymer Hybrids for Oxygen Reduction (pages 610–615)

      Kate R. Edelman, Keith J. Stevenson and Bradley J. Holliday

      Article first published online: 26 MAR 2012 | DOI: 10.1002/marc.201100784

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      Palladium nanoparticle (NP)/conducting polymer hybrid composites have been prepared by seeded growth and demonstrate electrocatalytic activity toward oxygen reduction, an important process in fuel cells. The metal center directly embedded in the conducting metallopolymer backbone serves as a seed point for size-controlled palladium NP growth.

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