ACS Publications. Most Trusted. Most Cited. Most Read
Synthesis and Redox Characterization of Phosphazene Terpolymers with Pendant Ferrocene Groups

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Macromolecules 2012, 45, 9, 3658-3668
    Article

    Synthesis and Redox Characterization of Phosphazene Terpolymers with Pendant Ferrocene Groups
    Click to copy article linkArticle link copied!

    View Author Information
    † Department of Chemistry, Duke University, Durham, North Carolina 27708, United States
    ‡ Department of Chemistry, Southern Methodist University, Dallas, Texas 75275, United States
    *E-mail: [email protected] (A.L.C.), [email protected] (P.W.-N.).
    Other Access OptionsSupporting Information (1)

    Macromolecules

    Cite this: Macromolecules 2012, 45, 9, 3658–3668
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ma300336e
    Published April 23, 2012
    Copyright © 2012 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    The synthesis, characterization, and electrochemistry of a series of five ferrocene-containing phosphazene terpolymers derived from the poly(alkyl/arylphosphazene) random copolymer, [(Ph)(Me)PN]0.6[Me2PN]0.4, 5, are described. The new terpolymers, 6 {[(Ph)(Me)PN]0.6[Me2PN]0.4}x{[(Ph){FcCH(OH)CH2}PN]0.6[(Me){FcCH(OH)CH2}PN]0.4}y, where Fc = (η5-C5H5)Fe(η5-C5H4) (6a, x = 0.50, y = 0.50; 6b, x = 0.60, y = 0.40; 6c, x = 0.65, y = 0.35; 6d, x = 0.70, y = 0.30; and 6e, x = 0.85, y = 0.15), were prepared by deprotonation–substitution reactions and were characterized by NMR spectroscopy, elemental analyses, gel permeation chromatography, and thermal analysis. The redox properties are described by electrochemistry performed in dichloromethane solutions and evaporatively cast films. In solution, cyclic voltammograms of these polymers display a one-electron reversible (ΔEp ca. 60 mV) wave in the range of 433–492 mV (vs Ag/AgCl) combined with adsorption, depending on the degree of substitution with Fc groups. The adsorption of the oxidized polymer on a Pt electrode was established using double potential step chronocoulometry. A mechanism for electron diffusion is discussed in terms of physical diffusion and electron hopping. The apparent electron diffusion coefficient was calculated from a combination method of chronocoulometry and rotating disk voltammetry. The observed diffusion coefficients are larger than those of corresponding polymers that contain a larger number of phenyl side groups and are largely independent of the degree of Fc substitution. A second, less intense wave about 220–250 mV more positive than the main wave was also observed and attributed to the internal oxidation of a secondary alcohol to a ketone group. Reversible electrochemical behavior of surface bound species is also observed for the ferrocene/ferricenium couple in evaporatively cast films of the phosphazene polymers. Cyclic voltammetry and chronoamperometry were used to determine the electrochemical characteristics and charge transport quantities (Γ and CD01/2) of the terpolymer films. These quantities vary with the degree of substitution with Fc groups of the phosphazene terpolymers.

    Copyright © 2012 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    Scanning electron micrographs and an additional figure. This material is available free of charge via the Internet at http://pubs.acs.org.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!

    This article is cited by 18 publications.

    1. Patty Wisian-Neilson Robert H. Neilson . Synthesis and Modification of Poly(alkyl/arylphosphazenes). 2018, 167-181. https://doi.org/10.1021/bk-2018-1298.ch008
    2. Sonia Bruña, Ignacio Martínez-Montero, Ana Ma González-Vadillo, Carlos Martín-Fernández, M. Merced Montero-Campillo, Otilia Mó, and Isabel Cuadrado . Ferrocene and Silicon-Containing Oxathiacrown Macrocycles and Linear Oligo-Oxathioethers Obtained via Thiol–Ene Chemistry of a Redox-Active Bifunctional Vinyldisiloxane. Macromolecules 2015, 48 (19) , 6955-6969. https://doi.org/10.1021/acs.macromol.5b01683
    3. Ignacio Martínez-Montero, Sonia Bruña, Ana Ma González-Vadillo, and Isabel Cuadrado . Thiol–Ene Chemistry of Vinylferrocene: A Simple and Versatile Access Route to Novel Electroactive Sulfur- and Ferrocene-Containing Model Compounds and Polysiloxanes. Macromolecules 2014, 47 (4) , 1301-1315. https://doi.org/10.1021/ma4025202
    4. Neşe Uzunalioğlu, Nuran Asmafiliz, Zeynel Kılıç, Tuncer Hökelek. Phosphorus-nitrogen compounds: Part 61. The novel sodium complexes of monoferrocenylspirocyclotriphosphaza-crown ethers. Inorganica Chimica Acta 2022, 539 , 121035. https://doi.org/10.1016/j.ica.2022.121035
    5. André Schäfer. Ferrocene and Related Metallocene Polymers. 2022, 3-22. https://doi.org/10.1016/B978-0-12-820206-7.00138-4
    6. Bikash kumar Sikder, Mutyala Naidu Ganivada, Tushar Jana. Functional Alkyl‐Ferrocene Grafted Hydroxyl Terminated Polybutadiene. ChemistrySelect 2021, 6 (31) , 8058-8062. https://doi.org/10.1002/slct.202101838
    7. Yanlin Shi, Michael J. Monteiro, Zhongfan Jia. Synthetic Strategies and Methods for Redox Polymers. 2020, 27-92. https://doi.org/10.1039/9781788019743-00027
    8. Moumita Dhara, Nitai Giri, Arunava Dutta, A.K. Patra, P.U. Sastry, Mahesh Shrikishan Ingole, Tushar Jana. Enhancing segmental compatibility and tuning the structure-property relationship in ferrocenylsilane tethered polyurethane. Polymer 2020, 204 , 122807. https://doi.org/10.1016/j.polymer.2020.122807
    9. Moumita Dhara, Nitai Giri, B. Narasimha Rao, A.K. Patra, P.U. Sastry, Mahesh Shrikishan Ingole, Tushar Jana. Effect of segmental compatibility imposed over metal based polybutadiene polyurethane. European Polymer Journal 2020, 122 , 109380. https://doi.org/10.1016/j.eurpolymj.2019.109380
    10. Jun Du, Wei Yuan, Haoke Zhang, Hongkun Li, Yongfang Li, Ben Zhong Tang. Ferrocene-based hyperbranched poly(phenyltriazolylcarboxylate)s: synthesis by phenylpropiolate-azide polycycloaddition and use as precursors to nanostructured magnetoceramics. Polymer Chemistry 2019, 10 (43) , 5931-5938. https://doi.org/10.1039/C9PY01375J
    11. Maria Cuartero, Robert G. Acres, Zdenka Jarolímová, Eric Bakker, Gaston A. Crespo, Roland De Marco. Electron Hopping between Fe 3 d States in Ethynylferrocene‐doped Poly(Methyl Methacrylate)‐poly(Decyl Methacrylate) Copolymer Membranes. Electroanalysis 2018, 30 (4) , 596-601. https://doi.org/10.1002/elan.201700510
    12. Shafqat Ali, Zareen Zuhra, Ian S. Butler, Sami Ullah Dar, Muhammad Usman Hameed, Dezhen Wu, Liqun Zhang, Zhanpeng Wu. High-throughput synthesis of cross-linked poly(cyclotriphosphazene-co-bis(aminomethyl)ferrocene) microspheres and their performance as a superparamagnetic, electrochemical, fluorescent and adsorbent material. Chemical Engineering Journal 2017, 315 , 448-458. https://doi.org/10.1016/j.cej.2017.01.049
    13. Serkan Yeşilot, Aylin Uslu. Stereochemical Aspects of Polyphosphazenes. Polymer Reviews 2017, 57 (2) , 213-247. https://doi.org/10.1080/15583724.2016.1191023
    14. Harry R. Allcock. Polyphosphazenes. 2017, 1-15. https://doi.org/10.1002/9781119951438.eibc0186.pub2
    15. Rudolf Pietschnig. Polymers with pendant ferrocenes. Chemical Society Reviews 2016, 45 (19) , 5216-5231. https://doi.org/10.1039/C6CS00196C
    16. Linxian Xu, Fan Yue, Wei Shi, Yonghai Hui, Hongyu Mi, Fudong Ma, Yong Tian, Zhengfeng Xie. A type of novel fluorescent phosphinimine derivative: Catalyst-free simple synthesis and optical properties. Dyes and Pigments 2013, 99 (3) , 822-828. https://doi.org/10.1016/j.dyepig.2013.07.010
    17. R. Senkuttuvan, V. Ramakrishna, K. Bakthavachalam, N. Dastagiri Reddy. Copper(I) and silver(I) complexes of carbaphosphazene-anchored N-heterocyclic carbene ligands. Journal of Organometallic Chemistry 2013, 723 , 72-78. https://doi.org/10.1016/j.jorganchem.2012.09.005
    18. Fumitoshi Kato, David A. Rider. Inorganic and organometallic polymers. Annual Reports Section "A" (Inorganic Chemistry) 2013, 109 , 277. https://doi.org/10.1039/c3ic90026f
    Download PDF
    Go to Macromolecules
    Get e-Alerts
    Get e-Alerts

    Macromolecules

    Cite this: Macromolecules 2012, 45, 9, 3658–3668
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ma300336e
    Published April 23, 2012
    Copyright © 2012 American Chemical Society
    Request reuse permissions

    Article Views

    976

    Altmetric

    -

    Citations

    18
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.