Stepwise introduction of three different transition metals in metallo-supramolecular polymer for quad-color electrochromism

Metallo-supramolecular polymers (MSPs) show unique electrochemical and optical properties, that are different to organic polymers, caused by electronic interactions between metals and ligands. For the development of quad-color electrochromic materials, here we report the stepwise introduction of three different transition metal ions into an MSP, utilizing the different complexation abilities of the transition metals. An MSP with Os(II), Ru(II), and Fe(II) (polyOsRuFe) was synthesized via a stepwise synthetic route through the formation of an Os(II) complex first, followed by the introduction of Ru(II) to the Os(II) complex, and finally the attachment of Fe(II) to the Os(II)-Ru(II) complex to produce the polymer. This synthetic procedure was extended to fabricate MSPs that comprised Co(II)/Ru(II)/Os(II) and Zn(II)/Ru(II)/Os(II). The synthesized MSPs showed a broad optical and electrochemical window due to the coupling of three heterometallic segments into the polymer. Introducing acetate anion as the counter anion greatly enhanced the solubility of polyOsRuFe in methanol. A thin film of polyOsRuFe was prepared on ITO/glass by spin-coating the methanol solution, and its reversible quad-color electrochromism was demonstrated.