Fe(II)-Based Metallo-Supramolecular Polymers

  • Masayoshi HiguchiEmail author
Part of the NIMS Monographs book series (NIMSM)


This chapter introduces synthesis, properties, and device application of Fe(II)-based metallo-supramolecular polymer (polyFeL1-5). Section 2.1 shows synthetic procedure of bis(terpyridine)s (L1-5) and preparation of polyFeL1-5 by the 1:1 complexation of Fe(II) ions with L1-5. Section 2.2 exhibits electrochemical and optical properties of polyFeL1-5. It is revealed that introduction of electron-releasing or -withdrawing groups to the ligand varies their polymer properties. Section 2.3 explains blue electrochromic properties of the polymers. PolyFeL1-5 have the metal-to-ligand charge transfer (MLCT) absorption from the Fe(II) ion to the terpyridine moiety at around 580 nm. Therefore, the color of the polymers is bluish, as the complementary color of the MLCT absorption. Authors found that the polymer film changes the color from blue to colorless upon applying an oxidative potential and the blue color recovered again upon applying a reductive potential. Section 2.4 introduces an electrochromic device fabrication using polyFeL1. Sections 2.5 show a hyperbranched structure formation by the further addition of Fe(II) ions and tris(terpyridine) to a solution of polyFeL1 and the improvement of electrochromic properties. Sections 2.6 exhibit another hyperbranched structure of metallo-supramolecular polymers and their ionic conductivity. Section 2.7 demonstrates electrochemical emission control of dye anions in an electrochemical device of polyFeL1.


Fe(II)-based metallo-supramolecular polymer Metal-to-ligand charge transfer absorption Blue electrochromism Hyperbranched structure Ionic conductivity Electrochemical emission switching 


  1. 1.
    Higuchi M, Kurth DG (2007) Electrochemical functions of metallo-supramolecular nano-materials. Chem Rec 7:203–209. Scholar
  2. 2.
    Han FS, Higuchi M, Kurth DG (2007) Diverse synthesis of novel bisterpyridines via suzuki-type cross-coupling. Org Lett 9:559–562. Scholar
  3. 3.
    Han FS, Higuchi M, Kurth DG (2007) Metallo-supramolecular polymers based on functionalized bis-terpyridines as novel electrochromic materials. Adv Mater 19:3928–3931. Scholar
  4. 4.
    Han FS, Higuchi M, Kurth DG (2008) Metallo-supramolecular polyelectrolytes self-assembled from various pyridine ring substituted bis-terpyridines and metal ions: photophysical, electrochemical and electrochromic properties. J Am Chem Soc 130:2073–2081. Scholar
  5. 5.
    Higuchi M, Akasaka Y, Ikeda T, Hayashi A, Kurth DG (2009) Electrochromic solid-state devices using organic-metallic hybrid polymers. J Inorg Organomet Polym Mater 19:74–78. Scholar
  6. 6.
    Higuchi M (2009) Electrochromic organic–metallic hybrid polymers: fundamentals and device applications. Polym J 41:511–520. Scholar
  7. 7.
    Higuchi M (2014) Stimuli-responsive metallo-supramolecular polymer films: design, synthesis and device fabrication. J Mater Chem C 2:9331–9341. Scholar
  8. 8.
    Hu CH, Sato T, Zhang J, Moriyama S, Higuchi M (2014) Three-dimensional Fe(II)-based metallo-supramolecular polymers with electrochromic properties of quick switching, large contrast, and high coloration efficiency. ACS Appl Mater Interfaces 6:9118–9125. Scholar
  9. 9.
    Pandey RK, Hossain MD, Sato T, Rana U, Moriyama S, Higuchi M (2015) Effect of a three-dimensional hyperbranched structure on the ionic conduction of metallo-supramolecular polymers. RSC Adv 5:49224–49230. Scholar
  10. 10.
    Suzuki T, Sato T, Zhang J, Kanao M, Higuchi M, Maki H (2016) Electrochemically switchable photoluminescence of an anionic dye in a cationic metallo-supramolecular polymer. J Mater Chem C 4:1594–1598. Scholar

Copyright information

© National Institute for Materials Science, Japan 2019

Authors and Affiliations

  1. 1.National Institute for Materials ScienceTsukubaJapan

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