We report the results of a combined work based on density functional theory (DFT) calculations and experiments of the factors that influence the glass temperature, T g , and the associated ion conductivity in polymerized ionic liquids bearing imidazolium salts in the side group. This study consists of four different N-alkyl side-chain lengths [with n = 4 (butyl), 6 (hexyl), 8 (octyl), and 10 (decyl)] and seven different counteranionsDFT calculations of the anion−cation complexation energies were combined with thermodynamics (differential scanning calorimetry), structural (X-ray scattering), as well as temperature-and pressure-dependent dielectric spectroscopy measurements of ion conduction. Our results show that ion conduction is facilitated by local anion jumps with a length scale on the order of the charge alteration distance. Ion complexation strongly influences the backbone dynamics and the associated T g . A simple "stick and jump" model can account for the increased backbone mobility (reduced T g ) and the concomitant enhanced ion conductivity for anions with intermediate size. Among the different anions, [TFSI] − with its comparably large size and broad charge delocalization is only weakly coordinated with the cation. This best facilitates anion motion within the "ion paths" of the hexagonally packed cylinders and smectic morphologies.

Single ion conductors, based on polymerized ionic liquids (PILs) with a polythiophene backbone bearing imidazolium salts with butyl, hexyl, octyl, and decyl side groups and six different counteranions ([Br]−, [BF4]−, [ClO4]−, [PF6]−, picrate, and [B­(Ph)4]−), are synthesized and studied with respect to the thermal, structural, and ion-conductivity properties. PILs bearing the polythiophene backbone are unique as they can simultaneously conduct electronic charge and ions at nanometer length scales. In addition, the π–π stacking of the polythiophene backbones results in exceptional smectic-like order. Increasing side group length from butyl to decyl increases the room temperature conductivity by 4 orders of magnitude (internal plasticization). Anion size (anionic radii from 0.19 to 0.44 nm) affects both the structure (from smectic-like to amorphous with increasing anion radius) and the ionic conductivity. Conductivity values differ by 6 orders of magnitude by varying anion size at ambient temperature. As a result, conductivities as high as 2 × 10–3 S/cm could be obtained at high temperatures. Differences in conductivity are discussed in terms of changes in glass temperature (T g), anion size, and value of dielectric permittivity. Overall ion transport in PILs based on polythiophene backbones is controlled by the low T g, value of dielectric permittivity, smectic layering, and ion association lengths not exceeding a single smectic layer.

Conjugated polymers exhibit strong interactions with single-walled carbon nanotubes (SWNTs). These enable the selective dispersion of specific semiconducting SWNTs in organic solvents and polymer-mediated energy transfer to the nanotubes followed by emission in the near-infrared. Conjugated polyelectrolytes with ionic side-chains can add further functionalities to these nanotube/polymer hybrids such as dispersibility in polar solvents (e.g., methanol) and self-doping. Here, we demonstrate and investigate energy transfer from a range of conjugated polymers to preselected (6,5) SWNTs with varying spectral overlap between the optical transitions of the polymer and nanotube. We find evidence for increased backbone planarization of the polymers wrapped around the nanotubes. Furthermore, ambient p-doping of hybrids of anionic conjugated polyelectrolytes and (6,5) SWNTs blocks energy transfer in contrast to cationic polyelectrolytes. By addition of a mild reducing agent, thus removing the p-doping, the energy transfer can be fully restored pointing toward an electron exchange mechanism. The p-doping of nanotube/polyelectrolyte hybrids in air and their doping-dependent emission and charge transport properties also become apparent in water-gated field-effect transistors based on such networks and might be useful for dual-signal sensing applications.

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