Triggerable Ion Release in Polymerized Ionic Liquids Containing Thermally Labile Diels–Alder Linkages

Abstract

Controlling the mobile ion content of ioncontaining polymers is critical for advanced organic electronic applications. Here, we report a chemical strategy for achieving "on-demand" release of ions in polymeric materials by incorporating thermally labile Diels−Alder linkages into polymerized ionic liquids. Electrical characterization demonstrates a clear increase in mobile ion content at the retro-Diels−Alder temperature, which is retained after the material is returned to room temperature. This work demonstrates that chemical triggers can be utilized to release ions and change the mobile ion content of a polymeric material after the sample is prepared, paving the way for new classes of responsive organic electronic devices.

Ion-Locking in Solid Polymer Electrolytes for Reconfigurable Gateless Lateral Graphene p-n Junctions

“…The results of the chemically locked, gateless, graphene p-n junction serve as proof-of-concept that alternate triggers can be used to semi-permanently dope 2D devices for room temperature operation. In fact, we have also recently shown that incorporation of thermally-labile linkers into polymerizable ionic liquids allows ions to be released after the materials are polymerized, which we anticipate will enable DPILs that can be locked and then unlocked with a second trigger [54]. This type of locking and unlocking-especially if it can be field-controlled-could prove useful for polymorphic circuits.…”

“…were synthesized according to reference [52][53][54]. One mg of the initiator, azobisisobutyronitrile (AIBN), was dissolved in 100 µL unpolymerized DPIL monomer, and then drop-cast in the glovebox (25 µL over 1 cm 2 ) with thickness estimated to bẽ 200 µm according to the cast volume.…”

“…Before polymerization, DPIL monomers behaved as a typical ionic liquid with mobile ions that can form EDLs in response to an applied field, Figure 4a. Once the ions were in place, heat was used to trigger DPIL polymerization, which immobilized the ions [54,61]. After polymerization, the programming voltages were removed, the device was cooled to room temperature, and transfer characteristics were made (Figure 4c).…”

A Review on Ionic Liquid Gas Separation Membranes

“…Chain growth polymerization (i) requires an IL monomer with an unsaturated or cyclic chemical structure that can be activated during the polymerization step ( Figure 5 ). Such a bond is often synthetically introduced into IL monomers (ILM) through the incorporation of methacrylic and methacrylamide [ 112 , 148 , 149 , 150 ], vinyl and styrene [ 116 , 151 , 152 , 153 , 154 , 155 ], or norbornene [ 156 , 157 , 158 ] or epoxy moieties. The sheer number of these reports demonstrates the applicability of this approach and underlines its advantages.…”

“…Initial reports of PILs synthesis emerged at the beginning of the 2000s and mostly employed conventional free radical polymerization (FRP) [ 159 , 160 ]. While allowing a straightforward preparation of PILs from monomers, it builds from pre-existing double bonds in methacrylate [ 149 , 161 ], vinyl- [ 155 , 161 , 162 , 163 , 164 ], and styrene [ 154 ] building blocks. In this case, the synthetic approach would include at least three steps to prepare a PIL with a halide anion: (i) Halide incorporation; (ii) quaternization; (iii) polymerization in the presence of an initiator (i.e., AIBN).…”