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Issue 8, 2018
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Terpyridine-functionalized stimuli-responsive microgels and their assembly through metal–ligand interactions

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Abstract

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-co-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 (Ni2+, Fe2+, Co2+, or Zn2+), and interestingly the assembled tpy-mG-M2+ showed different rheological properties depending on the metal ion type; the weakly bound ions (Co2+, Zn2+) indicated fast dynamics for “inter-particular” exchange, resulting in much higher storage (G′) and loss (G′′) moduli. Photocatalysts such as Ru dyes can be easily introduced into tpy-mGvia 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-Mg2+ 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 via reversible metal–ligand complexation.

Graphical abstract: Terpyridine-functionalized stimuli-responsive microgels and their assembly through metal–ligand interactions

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Publication details

The article was received on 04 Jan 2018, accepted on 30 Jan 2018 and first published on 30 Jan 2018


Article type: Paper
DOI: 10.1039/C8PY00016F
Citation: Polym. Chem., 2018,9, 1032-1039
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    Terpyridine-functionalized stimuli-responsive microgels and their assembly through metal–ligand interactions

    J. Lee, E. J. Choi, I. Varga, P. M. Claesson, S. Yun and C. Song, Polym. Chem., 2018, 9, 1032
    DOI: 10.1039/C8PY00016F

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