Melts of polybutylcarbosilane (PBC) dendrimers from third (G3) up to sixth (G6) generations are investigated by 1H NMR spectroscopy in a wide temperature range up to 493 K. At room temperature, NMR spectra of G3-G5 dendrimers exhibit resolved, solution-like spectra (“liquid” phase). In contrast, the spectrum of the G6 dendrimer is characterized by a single unresolved broad line at whole temperature range, which supports the presence of an anomalous phase state of G6 at temperatures higher than glass transition temperature. For the first time, an unexpected transition of G5 dendrimer from a molecular liquid state to an anomalous state/phase upon temperature increase has been detected using NMR data. Specifically, an additional wide background line appears in the G5 spectrum above 473 K, and this line corresponds to a G5 state characterized by restricted molecular mobility, i.e., a state similar to the “anomalous” phase of G6 melt. The fraction of the G5 dendrimers in “anomalous” phase at 493 K is approximately 40%. Analysis of the spectral shapes suggests that changes in the G5 dendrimers are reversible with temperature.

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Temperature dependences are compared for H and C NMR 1/T curves relaxation rates in three imidazolium-based ionic liquids (ILs), namely, in [bmim]PF , [bmim]BF , and [emim]CH COO. C curves show alike behavior for all three ILs and follow a well-known Bloembergen-Pound-Purcell (BPP) equation. On the contrary, an essential part of H curves differ strongly from corresponding C ones and also have different shapes for different ILs. For the first time, we have detected the specific, two-maximum shape of H relaxation curve for hydrogen atom of C(2)H group of the [emim]CH COO. Assuming that this maximum reflects the correlated rotation of several adjoining ion pairs, we have tried to destroy this rotation by addition of glycerol to the [emim]CH COO. The second, high-temperature maximum has disappeared in the [emim]CH COO-glycerol mixture, and this fact confirms our assumption. Copyright © 2017 John Wiley & Sons, Ltd.

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Ionic liquids (ILs) have a wide variety of applications in modern electrochemistry due to their unique electrolytic properties. In particular, they are promising candidates as dopants for polymeric membranes in potentiometric sensors and liquid-junction free reference electrodes. However, the effective use of ILs requires a comprehensive understanding of their electrolytic behavior in the polymeric phase. We report here the exploration of the electrolytic and diffusion properties of IL 1-hexyl-3-methyl-1H-imidazol-3-ium bis[(trifluoromethyl)sulfonyl]amide ([C6Meim][NTf2]) in a poly(vinyl chloride) matrix. Chronopotentiometry is utilized to determine the concentration of charge carriers, ionic diffusion coefficients and apparent dissociation constant of [C6Meim][NTf2] in PVC membranes plasticized with a mixture of [C6Meim][NTf2] and bis(2-ethylhexyl) sebacate (DOS) over a wide range of IL concentrations. The diffusion properties of [C6Meim][NTf2] are confirmed by NMR-diffusometry. The non-monotonic electrolytic behavior of the IL in PVC−DOS matrix is described for the first time. A maximum ionization degree and diffusion coefficient is observed at 30 wt.% of IL in the plasticizing mixture. Thus, it is shown that by varying the flexible parameter of the IL to plasticizer ratio in the polymeric phase one can tune the electrolytic and transport properties of sensing PVC membranes.