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Lee, Jookyeong,Choi, Eun Jung,Varga, Imre,Claesson, Per M.,Yun, Sang-Ho,Song, Changsik The Royal Society of Chemistry 2018 Polymer chemistry Vol.9 No.8
<P>We developed a terpyridine-functionalized microgel (tpy-mG) for its supramolecular assembly. Tpy-mG was synthesized by amidation between 3-(4-([2,2′:6′,2′′-terpyridin]-4′-yl)phenoxy)propan-1-amine and carboxylates of a thermo-responsive p(NIPAM-<I>co</I>-MAA) microgel (A-mG), which was synthesized by emulsion polymerization. After decorating terpyridine, its effects on the hydrodynamic radius, volume phase transition temperature (VPTT), and the colloidal stability of the microgel were investigated. Tpy-mG can be assembled reversibly with several metal ions (Ni<SUP>2+</SUP>, Fe<SUP>2+</SUP>, Co<SUP>2+</SUP>, or Zn<SUP>2+</SUP>), and interestingly the assembled tpy-mG-M<SUP>2+</SUP> showed different rheological properties depending on the metal ion type; the weakly bound ions (Co<SUP>2+</SUP>, Zn<SUP>2+</SUP>) indicated fast dynamics for “inter-particular” exchange, resulting in much higher storage (<I>G</I>′) and loss (<I>G</I>′′) moduli. Photocatalysts such as Ru dyes can be easily introduced into tpy-mG<I>via</I> metal-ligand interactions, and the photooxidation of benzylamine was tested. The free Ru dye showed almost the same conversions at 25 and 50 °C, whereas the assembled Ru-tpy-mG-Mg<SUP>2+</SUP> displayed reduced conversion at 50 °C (>VPTT). This is suggested to be due to the collapsed or “locked” structure around the photocatalytic center (Ru). Tpy-mG can be utilized as a good platform for developing responsive functional materials <I>via</I> reversible metal-ligand complexation.</P>