Light-mediated CO2-responsiveness of metallopolymer microgels

Abstract

Here, we report a finding on light-mediated CO2-responsiveness. It is found on the microgels that are made of side-chain type metallopolymers containing metalla-aromatics. Turbidity and laser light scattering studies on dilute aqueous dispersion of these microgels in dark indicate high CO2-responsivity, but poor reversibility upon N2 purge, which can be improved by exposing to light. This light-mediated CO2-responsiveness can be elucidated by the loss of aromaticity from initial photoexcitation and concurrent formation of a less reactive, antiaromatic excited state of relatively low CO2 binding affinity, and by subsequent relief of antiaromaticity that can enhance the CO2 removal. The finding is also checked by CO2 uptake-release experiments on the microgels, which enables both CO2 capture of high capacity and CO2 removal of good reversibility under a mild condition, allowing effective and reversible response to dilute CO2.