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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
Published on: March 24, 2018
Structural Dynamics of Temperature- and Pressure-Induced Phase Transitions in Hybrid Imidazolium Lead Chlorides
Szymon Smółka1, Dawid Drozdowski1, Dagmara Stefańska1
1Polish Academy of Sciences, Institute of Low Temperature and Structure Research, Okólna 2, 50-422 Wrocław, Poland.
Abstract:
We report the synthesis and comprehensive characterization of two previously unreported imidazolium lead chlorides, IM2Pb3Cl8·0.5H2O and IM3PbCl5, establishing chloride analogues as a platform to interrogate how inorganic-framework dimensionality and hydrogen-bond topology control structure, dynamics, and functional response in hybrid lead halides. Single-crystal X-ray diffraction reveals that IM3PbCl5 consists of one-dimensional corner-sharing [PbCl5]n3- chains, whereas IM2Pb3Cl8·0.5H2O adopts a three-dimensional porous framework constructed from edge- and face-sharing PbCl8 polyhedra hosting IM+ cations and water molecules. Variable-temperature calorimetry, diffraction, and Raman spectroscopy show that IM3PbCl5 undergoes a sequence of first-order phase transitions driven by progressive ordering of the imidazolium sublattice coupled to distortions of the inorganic chains and reorganization of N-H···Cl contacts; hydrostatic compression induces three additional transitions at elevated pressures. In contrast, IM2Pb3Cl8·0.5H2O shows no thermal anomalies in the investigated range and exhibits smaller pressure-induced shifts of selected phonon modes. Dielectric spectroscopy indicates thermally activated imidazolium reorientations and ionic transport at elevated temperatures, while optical measurements indicate wide band gaps and intense broadband emission in the spectral range from Vis to NIR.
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