Dual Free Radical Synergism for Enhancing Proton Conductivity in Photochromism iHOFs

Stimuli-responsive smart materials, as an emerging material, can fulfill reversible transformation of chemical/physical properties under external stimuli such as mechanical stress, light, and electricity, which has the highlights of rapid response, designable structure, and function. Two ionic hydrogen-bonded organic frameworks (<b>iHOFs 36-37</b>) were synthesized by self-assembly of bis(benzene-<i>o</i>/<i>p</i>-sulfonic acid)-naphthalenediimide (<i>o</i>/<i>p</i>-H₂BSNDI) and two basic ligands. The naphthalenediimide (NDI) was introduced into the material to equip <b>iHOFs 36-37</b> with radical-driven photochromic behavior. The proton conductivity of <b>iHOF-37</b> demonstrated a maximum of 6.50 × 10^-4 S·cm^-1 at 98% RH and 100 °C, and it increased to 9.10 × 10^-3 S·cm^-1 due to dual free radical synergism following UV irradiation (NDI and viologen), which represents a significant 14-fold enhancement. Furthermore, the incorporation of <b>iHOF-37</b> into the chitosan (CS) matrix forms photochromic composite membranes. The proton conductivity of the <b>5%-iHOF-37/CS</b> composite membrane reached up to 5.70 × 10^-2 S·cm^-1 at 98% RH and 90 °C, and reached 8.08 × 10^-2 S·cm^-1 after UV irradiation. This work reveals the dual radicals generated by NDI and viologen derivatives, whose synergistic action plays a significant role in enhancing the proton conductivity in iHOFs and composite membranes, rendering the rational design of stimuli-responsive smart materials feasible.