Highly Efficient and Reversible Iodine Capture in Hexaphenylbenzene-Based Conjugated Microporous Polymers

The effective and safe capture and storage of radioactive iodine (¹²⁹I or ¹³¹I) is of significant importance during nuclear waste storage and nuclear energy generation. Here we present detailed evidence of highly efficient and reversible iodine capture in hexaphenylbenzene-based conjugated microporous polymers (HCMPs), synthesized via Buchwald–Hartwig (BH) cross-coupling of a <i>hexakis</i>(4-bromophenyl)benzene (HBB) core and aryl diamine linkers. The HCMPs present moderate surface areas up to 430 m² g⁻¹, with narrow pore size distribution and uniform ultra-micropore sizes of less than 1 nm. Porous properties are controlled by the strut lengths and rigidities of linkers, whilst porosity and uptake properties can be tuned by changing the oxidation state of the HCMPs. The presence of a high number of amine functional groups combined with microporosity provides the HCMPs with extremely high iodine affinity with uptake capacities up to 316 wt%, which is, to the best of our knowledge, the highest reported to date. Two ways to release the adsorbed iodine were explored: either slow release into ethanol or quick release upon heating (with a high degree of control). Spectral studies indicate that the combination of microporosity, amine functionality and abundant π-electrons ensured well-defined host−guest interactions and controlled uptake of iodine. In addition, the HCMPs could be recycled whilst maintaining 90% iodine uptake capacity (up to 295%). We envisage wider application of these materials in the facile uptake and removal of unwanted oxidants from the environment.