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Cu(II)-Based Metallo-Supramolecular Polymers

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

Abstract

This chapter introduces synthesis and green electrochromism of Cu(II)-based metallo-supramolecular polymers (polyCuL10-15) and synthesis and multi-color electrochromism of Cu(I)/Fe(II)-based heterometallo-supramolecular polymer (polyCuFeL16). To introduce Cu(II) ions with a tetrahedral structure into metallo-supramolecular polymers, 5,5′-linked bis(1,10-phenanthroline)s (L10-15) are synthesized by a Suzuki-type cross-coupling reaction. Section 6.1 introduces optimization to the synthetic conditions (catalyst, based, solvent, and temperature) of L10-15 and the detailed synthetic procedure for polyCuL13 by the 1:1 complexation of L13 and Cu(ClO4)2·6H2O. Section 6.2 shows stepwise complexation behavior of L13 with Cu(II) ions and green electrochromism of polyCuL13. The green color of polyCuL13, which is caused by the MLCT absorption of the Cu(II) complex moieties, disappears upon applying a negative potential because of the electrochemical reduction of Cu(II) to Cu(I). Section 6.3 describes synthesis of Cu(I)/Fe(II)-based heterometallo-supramolecular polymer (polyCuFe16) by one-pot complexation of Cu(I), Fe(II), and an asymmetrical ligand (L16). L16 has both bidentate phenanthroline and tridentate terpyridine moieties. Cu(I) and Fe(II) ions are preferentially complexed with the bidentate phenanthroline and tridentate terpyridine moieties of L16, respectively, based on the different (tetrahedral or octahedral) coordination geometries. Section 6.4 shows multi-color electrochromism (from purple to blue to colorless) in a solid-state device with a polyCuFeL16 film.

Keywords

Cu(II)-based metallo-supramolecular polymer Stepwise complexation Green electrochromism Cu(I)/Fe(II)-based heterometallo-supramolecular polymer Multi-color electrochromism 

References

  1. 1.
    Hossain MD, Sato T, Higuchi M (2013) Green color copper-based metallo-supramolecular polymer: synthesis, structure, and electrochromic properties. Chem Asian J 8:76–79.  https://doi.org/10.1002/asia.201200668CrossRefPubMedGoogle Scholar
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    Hossain MD, Higuchi M (2013) Synthesis of metallo-supramolecular polymers using 5,5′-linked bis(1,10-phenanthroline) ligands. Synthesis 45:753–758.  https://doi.org/10.1055/s-0032-1316858CrossRefGoogle Scholar
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    Hossain MD, Zhang J, Pandey RK, Sato T, Higuchi M (2014) A heterometallo-supramolecular polymer with CuI and FeII ions introduced alternately. Eur J Inorg Chem 2014:3763–3770.  https://doi.org/10.1002/ejic.201402468CrossRefGoogle Scholar

Copyright information

© National Institute for Materials Science, Japan 2019

Authors and Affiliations

  1. 1.National Institute for Materials ScienceTsukubaJapan

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