Macromolecular Rapid Communications

Cover image for Vol. 31 Issue 9‐10

Special Issue: Metal-Containing and Metallo-Supramolecular Polymers and Materials

May 12, 2010

Volume 31, Issue 9-10

Pages 763–938

Issue edited by: S. Hornig, I. Manners, G. R. Newkome, U. S. Schubert

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Review
    6. Feature Articles
    7. Communications
    8. Back Cover
    1. Macromol. Rapid Commun. 9-10/2010

      Qiang Zhao, Shu-Juan Liu and Wei Huang

      Article first published online: 17 MAY 2010 | DOI: 10.1002/marc.201090022

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      Front Cover: The picture presents the beautiful night scenes of the Nanjing (P. R. China) due to all kinds of light sources. Polymers containing phosphorescent iridium(III) complexes, as a class of excellent light-emitting materials, are promising for applications in solid-state lighting. In addition, such materials have also been applied successfully in light-emitting devices for displays. Further details can be found in the article by Qiang Zhao, Shu-Juan Liu, and Wei Huang*on page 794.

  2. Contents

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Review
    6. Feature Articles
    7. Communications
    8. Back Cover
    1. Macromol. Rapid Commun. 9-10/2010 (pages 763–769)

      Article first published online: 17 MAY 2010 | DOI: 10.1002/marc.201090023

  3. Editorial

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Review
    6. Feature Articles
    7. Communications
    8. Back Cover
    1. Metal-Containing and Metallo-Supramolecular Polymers and Materials (page 771)

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

      Article first published online: 21 APR 2010 | DOI: 10.1002/marc.201000196

  4. Review

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Review
    6. Feature Articles
    7. Communications
    8. Back Cover
    1. Poly(ferrocenylsilane) Gels and Hydrogels with Redox-Controlled Actuation (pages 772–783)

      Mark A. Hempenius, Concetta Cirmi, Fabio Lo Savio, Jing Song and G. Julius Vancso

      Article first published online: 16 APR 2010 | DOI: 10.1002/marc.200900908

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      Poly(ferrocenylsilane) (PFS)-based organometallic gels and hydrogels form a novel class of redox-responsive materials. These networks are swellable in organic solvents or in water, depending on the substituents attached to PFS. Chain properties such as charge density and interaction with surrounding solvent may be reversibly controlled by redox in a continuous manner, enabling applications such as photonic crystal full color displays or actuators.

  5. Feature Articles

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Review
    6. Feature Articles
    7. Communications
    8. Back Cover
    1. Metal–Ligand-Containing Polymers: Terpyridine as the Supramolecular Unit (pages 784–793)

      Raja Shunmugam, Gregory J. Gabriel, Khaled A. Aamer and Gregory N. Tew

      Article first published online: 4 MAY 2010 | DOI: 10.1002/marc.200900869

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      Terpyridine-complex containing homopolymers (left) and block copolymers (right) behaved as rigid-rod-like molecules due to the increase in persistence length generated by the metal complex. This leads to interesting self-assembling including hierarchical length scales in the block copolymer.

    2. Promising Optoelectronic Materials: Polymers Containing Phosphorescent Iridium(III) Complexes (pages 794–807)

      Qiang Zhao, Shu-Juan Liu and Wei Huang

      Article first published online: 12 MAR 2010 | DOI: 10.1002/marc.200900888

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      As one of the most promising optoelectronic materials, polymers that contain phosphorescent IrIII complexes have attracted more and more interest in recent years. They have been applied successfully in polymer light-emitting diodes. In this article, the design principles, synthetic routes, structure–property relationships, and applications in optoelectronic devices of polymers that contain phosphorescent IrIII complexes are summarized.

    3. Luminescent Coordination Polymers Built Upon Cu4X4 (X=Br,I) Clusters and Mono- and Dithioethers (pages 808–826)

      Pierre D. Harvey and Michael Knorr

      Article first published online: 11 MAY 2010 | DOI: 10.1002/marc.200900893

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      This paper focuses on the syntheses, structures, and luminescence properties of 1D, 2D, and 3D coordination polymers built upon the tetranuclear Cu4X4 clusters and mono- and dithioether assembling ligands. A review of the relevant literature is presented along with our own results stressing on the salient features of the interactions between the CuI salt as the starting material and the thioethers.

  6. Communications

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Review
    6. Feature Articles
    7. Communications
    8. Back Cover
    1. RAFT Polymerization Meets Coordination Chemistry: Synthesis of a Polymer-Based Iridium(III) Emitter (pages 827–833)

      Christoph Ulbricht, Caglar Remzi Becer, Andreas Winter and Ulrich S. Schubert

      Article first published online: 24 MAR 2010 | DOI: 10.1002/marc.200900787

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      Well-defined copolymers containing phosphorescent iridium(III) emitters can be obtained by reversible addition fragmentation chain-transfer polymerization, followed by coordination of a reactive iridium(III) precursor complex to the ligand sites on the polymer chain under very mild conditions.

    2. Aggregation-Induced Emission in a Hyperbranched Poly(silylenevinylene) and Superamplification in Its Emission Quenching by Explosives (pages 834–839)

      Ping Lu, Jacky W. Y. Lam, Jianzhao Liu, Cathy K. W. Jim, Wangzhang Yuan, Ni Xie, Yongchun Zhong, Qin Hu, Kam Sing Wong, Kevin K. L. Cheuk and Ben Zhong Tang

      Article first published online: 6 APR 2010 | DOI: 10.1002/marc.200900794

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      A hyperbranched poly(silylenevinylene) with high solubility and stability is synthesized by alkyne polyhydrosilylation. The polymer shows an aggregation-induced emission effect and works as an excellent chemosensor for explosive detection.

    3. Supramolecular Star-Shaped Poly(ethylene glycol) Based on a [2 × 2] Grid-Like Metal Complex (pages 840–845)

      Richard Hoogenboom, Brian C. Moore and Ulrich S. Schubert

      Article first published online: 4 MAR 2010 | DOI: 10.1002/marc.200900834

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      Supramolecular star-shaped polymers are an interesting class of materials that combine the properties of star-shaped polymers and supramolecular interactions. Here, we report a supramolecular star-shaped poly(ethylene glycol) based on a [2 × 2] copper(I) grid of 3,6-di(2-pyridyl)-pyridazine (DPP) as structural motif to form the core of supramolecular star-shaped polymers.

    4. Organometallic Complexes for Nonlinear Optics, 47 – Synthesis and Cubic Optical Nonlinearity of a Stilbenylethynylruthenium Dendrimer (pages 846–849)

      Christopher J. Jeffery, Marie P. Cifuentes, Gulliver T. Dalton, T. Christopher Corkery, Michael D. Randles, Anthony C. Willis, Marek Samoc and Mark G. Humphrey

      Article first published online: 12 MAR 2010 | DOI: 10.1002/marc.200900859

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      The 1st generation stilbenylethynylruthenium dendrimer shown here is prepared by a synthetic route that exploits Emmons–Horner–Wadsworth coupling of metal ethynyl-functionalized benzaldehyde. Its molecular weight-scaled refractive nonlinearity is significantly larger than that of its zero-generation analog, an NLO dendritic effect. In contrast to its all-ethynyl-linked analog, it is a nonlinear absorber at telecommunications wavelengths.

    5. Shape-Persistent, Truxene-Based, Nano-Sized Bisterpyridine Ruthenium(II) Complexes: Synthesis and Photophysical Properties (pages 850–855)

      Jin-Liang Wang, Yi-Tsu Chan, Charles N. Moorefield, Jian Pei, David A. Modarelli, Natalie C. Romano and George R. Newkome

      Article first published online: 19 MAR 2010 | DOI: 10.1002/marc.200900874

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      A new series of shape-persistent metallomacromolecules G0 and G1, based on thiophene-functionalized bisterpyridine-Ru(II) with truxene moieties are synthesized. These branched structures result in higher molar absorption coefficient and broader absorption making these macromolecules stable potential candidates for dye-sensitized solar cells.

    6. Synthesis of Prussian Blue Coordination Polymer Nanocubes via Confinement of the Polymerization Field Using Miniemulsion Periphery Polymerization (MEPP) (pages 856–860)

      Ronan McHale, Negar Ghasdian, Yibo Liu, Huihui Wang, Yuqing Miao and Xiaosong Wang

      Article first published online: 6 APR 2010 | DOI: 10.1002/marc.200900875

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      Miniemulsion periphery polymerization (MEPP) has been used for the synthesis of Prussian blue (PB) nanocubes The combination of pentacyano ferrate functionalized surfactant (EPE-Fe; 60% by weight) and additional surfactants without ferrate end group (40% by weight) is required for the formation of cubic morphology. Particles with irregular shape have been observed by reacting EPE-Fe and Fe3+ directly in water.

    7. Very-Low-Bandgap Metallopolyynes of Platinum with a Cyclopentadithiophenone Ring for Organic Solar Cells Absorbing Down to the Near-Infrared Spectral Region (pages 861–867)

      Xing-Zhu Wang, Qiwei Wang, Lei Yan, Wai-Yeung Wong, Kai-Yin Cheung, Annie Ng, Aleksandra B. Djurišić and Wai-Kin Chan

      Article first published online: 1 MAR 2010 | DOI: 10.1002/marc.200900885

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      Very-low-bandgap platinum metallopolyynes of cyclopentadithiophenone derivatives and their molecular model complexes are reported. Polymers P1 and P2 have respective optical bandgaps of 1.53 (blue) and 1.44 eV (green), which are much lowered relative to that for P0 (2.55 eV, yellow). The incorporation of an electron-accepting keto bridge on the oligothiophene ring in the main chain furnishes a new π-conjugated donor–acceptor system with near-infrared absorption appropriate for photovoltaic cells.

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      π-Conjugated Donor and Donor–Acceptor Metallo-Polymers (pages 868–874)

      Andreas Wild, Florian Schlütter, Georges M. Pavlov, Christian Friebe, Grit Festag, Andreas Winter, Martin D. Hager, Vera Cimrová and Ulrich S. Schubert

      Article first published online: 16 APR 2010 | DOI: 10.1002/marc.200900889

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      The reaction of donor and/or acceptor containing π-conjugated bisterpyridines with zinc(II) and ruthenium(II) ions results in a series of metallo homo and copolymers. The characterization using SEC, analytical AUC, and viscosimetry prove the ruthenium(II) metallo-polymers to be high molar mass materials (Mfs = 20 000 g · mol−1, equation image = 38 000 g · mol−1 Ru1-2; Mfs = 34 000 g · mol−1, equation image = 88 000 g · mol−1 Ru1) exhibiting intrinsic viscosities of up to [η] = 192 cm3 · g−1.

    9. Conjugated Copolymers Containing Low Bandgap Rhenium(I) Complexes (pages 875–882)

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

      Article first published online: 6 APR 2010 | DOI: 10.1002/marc.200900890

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      Conjugated polymers containing low bandgap rhenium(I) complexes on the main chain with the optical absorption extended to the near-infrared region are reported. Their photophysical, electrochemical, and photovoltaic properties were also investigated.

    10. Dual Emission from Highly Conjugated 2,2′:6′:2″-Terpyridine Complexes—A Potential Route to White Emitters (pages 883–888)

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

      Article first published online: 19 MAR 2010 | DOI: 10.1002/marc.200900894

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      Dual luminescence from transition-metal terpyridine complexes opens a doorway for supramolecular white emitters with the potential of tuning the spectral properties by tailoring the electronic coupling between various excited states by structural design of the terpyridine ligand.

    11. Silacyclobutane-Based Diblock Copolymers with Vinylferrocene, Ferrocenylmethyl Methacrylate, and [1]Dimethylsilaferrocenophane (pages 889–896)

      Markus Gallei, Stefan Tockner, Roland Klein and Matthias Rehahn

      Article first published online: 6 APR 2010 | DOI: 10.1002/marc.200900897

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      Three ferrocene-based monomers are shown to be valuable starting materials for creating block copolymers with different silacyclobutanes. The applied living anionic polymerization guarantees high blocking efficiencies as well as narrow block-length and molar-mass distributions. The microphase-separated materials are expected to be valuable precursors of novel functional macromolecules and smart ceramics.

    12. Monte Carlo Simulations of Metallo-Supramolecular Micelles (pages 897–903)

      Shihu Wang and Elena E. Dormidontova

      Article first published online: 4 MAR 2010 | DOI: 10.1002/marc.200900900

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      The equilibrium properties of metallo-supramolecular micelles are studied by computer simulations as a function of aggregation number, association energy and corona block length. We found that with an increase of aggregation number the area per corona-block attached to the core decreases, while the fraction of 2:1 ligand metal complexes in the bulk and 1:1 ligand metal complexes on the surface increases.

    13. Electropolymerization of a Ruthenium(II) Bis(pyrazolyl)pyridine Complex to Form a Novel Ru-Containing Conducting Metallopolymer (pages 904–909)

      Xun Jin Zhu and Bradley J. Holliday

      Article first published online: 6 APR 2010 | DOI: 10.1002/marc.200900902

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      A new metal-containing conducting metallopolymer was deposited directly on electrode surfaces as a transparent, deep red film by electrochemical coupling reaction. The metal complex is located directly in the conjugated backbone of the polymer and displays strong electronic interactions between the organic bridge and metal center. Additionally, the Ru(bpp)(terpy)2+ moieties enhance the photosensitivity of the conducting metallopolymer in the visible region.

    14. Photooxidation of Nanopatterned Poly(chloromethylstyrene): Direct Formation of Crosslinked Aldehyde-Functionalized Films for Chemical Functionalization and Bioconjugation (pages 910–914)

      Xi Yu, Chandramouleeswaran Subramani, Xiaochao Yang, Chae Kyu Kim and Vincent M. Rotello

      Article first published online: 19 MAR 2010 | DOI: 10.1002/marc.200900925

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      Aldehyde groups generated upon UV irradiation of chloromethyl styrene are utilized as surface active groups for polymer surface functionalization through aldehyde-amine chemistry. Using this method, we successfully activate the inert nanoimprint polymer resist pattern, allowing facile immobilization of dyes, nanoparticles, and enzymes onto the pattern. The processes were characterized by attenuated total reflection infrared (ATR-IR), X-ray photoelectron spectroscopy (XPS), and fluorescence microscopy.

    15. Donor–π–Acceptor Polymer with Alternating Triarylborane and Triphenylamine Moieties (pages 915–920)

      Haiyan Li and Frieder Jäkle

      Article first published online: 30 APR 2010 | DOI: 10.1002/marc.200900932

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      The organoboron donor–π–acceptor polymer (image) is strongly luminescent in solution and the solid state. Electronic communication between nitrogen and boron is pronounced according to electrochemical studies, and a distinct solvatochromic effect is indicative of the charge-transfer character of the emission. The luminescence was effectively quenched upon exposure to fluoride and cyanide suggesting potential use as a probe for anions.

    16. Complexation of Terpyridine-Containing Dextrans: Toward Water-Soluble Supramolecular Structures (pages 921–927)

      Andreas Wild, Stephanie Hornig, Florian Schlütter, Jürgen Vitz, Christian Friebe, Martin D. Hager, Andreas Winter and Ulrich S. Schubert

      Article first published online: 21 APR 2010 | DOI: 10.1002/marc.201000010

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      A water-soluble dextran-PEG comb-polymer was synthesized by complexation of a terpyridine functionalized dextran ester with a terpyridine RuII complex functionalized with PEG. Different degrees of substitution of the terpyridine dextran ester were obtained easily, and the complexation behavior was studied in detail using UV–vis titration and viscosimetry titration both utilizing FeII ions. The hydrophobic terpyridine functionalized dextrans can be further formulated into nanospheres.

    17. Seeded Growth and Solvent-Induced Fragmentation of Fiberlike Polyferrocenylsilane–Polyisoprene Block Copolymer Micelles (pages 928–933)

      Jieshu Qian, Gerald Guerin, Graeme Cambridge, Ian Manners and Mitchell A. Winnik

      Article first published online: 17 MAY 2010 | DOI: 10.1002/marc.201000092

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      Addition of THF, a common good solvent, to a solution of PI1000–PFS50 block copolymer micelles in decane leads to broadening of the length distribution. Instead of promoting dissociation of polymer molecules from the ends of the micelles, the THF induces the fragmentation of the micelles.

    18. Fiberlike Micelles Formed by Living Epitaxial Growth from Blends of Polyferrocenylsilane Block Copolymers (pages 934–938)

      Graeme Cambridge, Gerald Guerin, Ian Manners and Mitchell A. Winnik

      Article first published online: 17 MAY 2010 | DOI: 10.1002/marc.201000104

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      Polyferrocenylsilane (PFS) block copolymers form rodlike micelles in selective solvents by a seeded growth mechanism. Micelles of four different PFS block copolymers were grown from suspensions of a common seed micelle. The length of the micelles varied with the nature of the corona-forming block.

  7. Back Cover

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Review
    6. Feature Articles
    7. Communications
    8. Back Cover
    1. Macromol. Rapid Commun. 9-10/2010

      Richard Hoogenboom, Brian C. Moore and Ulrich S. Schubert

      Article first published online: 17 MAY 2010 | DOI: 10.1002/marc.201090024

      Thumbnail image of graphical abstract

      Back Cover: The image presents the self-assembly of polymeric precursors to form supramolecular star-shaped polymers. Supramolecular star-shaped polymers are an interesting class of materials that combine the properties of star-shaped polymers and supramolecular interactions. Further details can be found in the article by Richard Hoogenboom,* Brian C. Moore, and Ulrich S. Schubert*on page 840.

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