We have prepared a series of new ionically conducting polymer electrolytes consisting of side-chain liquid crystal terpolymers with mesogenic azobenzenes, sulfonic acid groups and methyl methacrylate. The poly[10-(4-methoxyazobenzene-4'-oxy)decyl methacrylate]-copoly[2-acrylamido-2-methyl-1-propanesulfonic acid]-co-poly[methyl methacrylate]s, 10-MeOAzB/AMPS/MMA terpolymers, were synthesised by a one-pot conventional radical polymerisation. All samples were characterised by NMR, GPC/SEC, FT-IR, POM, XRD, DSC, UV-visible spectrophotometry and EIS. The terpolymers have light responsive properties, and exhibit liquid crystallinity over a wide range of compositions. Above a certain threshold of AMPS content, the 10-MeOAzB/AMPS/MMA terpolymers exhibit ionic conductivities in the 10-8-10-4 S cm-1 range, with signs of decoupling of ionic mobility from segmental motions of the polymer.

We assess the assembly of supramolecular complexes by hydrogen bonding between azocompounds and a diacylaminopyridine monomer by temperature-dependent Fourier transform infrared spectroscopy (FT-IR) and density functional theory (DFT) calculations. The electronic delocalisation in the supramolecular rings formed by multiple hydrogen bonds stabilises the complexes, which coexist with dimeric species in temperature-dependent equilibria. We show how the application of readily available molecular modelling and spectroscopic techniques can predict the stability of new supramolecular entities coexisting in equilibria, ultimately assessing the success of molecular recognition.

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