Bias-Field and Pressure Effects on the One-Dimensional Dielectric Response in N−H+···N Hydrogen-Bonded 1,4-Diazabicyclo[2.2.2]octane Hydrobromide Crystal

Abstract

Unusual dielectric properties of 1,4-diazabicyclo[2.2.2]octane hydrobromide [C(6)H(13)N(2)](+).Br(-) (dabcoHBr) have been investigated at ambient and hydrostatic pressures and at biasing dc electric field. The crystal exhibits a huge dielectric constant along the hydrogen-bonded chains, exceeding 1500, while in the perpendicular direction it behaves as a typical nonpolar dielectric. Though the dynamics of protons in the N-H(+)...N hydrogen bonds is essential for these properties, of key importance are weak protonic correlations leading to the formation of short-range ordered regions. The complex dielectric response of dabcoHBr is due to several contributions involving dipolar fluctuation within the polar nanoregions, fluctuations of boundaries, and excitation of solitonic kinks propagating along the chains as a result of coherent proton transfers. A relatively low dc biasing electric field distinctly modifies the dielectric response, making it reminiscent of ferroelectric relaxors. Profound changes are also induced by hydrostatic pressure, which counteracts the proton correlations and the short-range polar order formation. At elevated pressures, the hexagonal structure of dabcoHBr undergoes a phase transition, associated with a loss of the unusual dielectric properties. This is due to the breaking of the N-H(+)...N hydrogen bonds, which destroys the one-dimensional topology of the polycationic chains and results in formation of the phase built of hydrogen-bonded ionic pairs. The phase diagram, illustrating the phase boundary between the high- and low-dielectric constant phases of dabcoHBr, is presented.