Abstract
Multiple crystal pathways and crystal polymorphs were observed in protic ionic liquids (pILs), which are liquid or solid at room temperature. The pILs studied were methylammonium nitrate (MAN), dimethylammonium nitrate (DAN), ethylammonium nitrate (EAN), and propylammonium nitrate (PAN). MAN and DAN solidified as plastic crystals at room temperature, whereas EAN and PAN are liquids at room temperature. Solid MAN and DAN indicated crystal polymorphs. In spite of its simple molecular structure, complicated phase behaviors such as multiple crystal pathways and crystal polymorphs were observed in liquid EAN at low temperature [Abe et al., J. Mol. Liq. 241 (2017) 301]. Liquid PAN also possesses low-temperature anomalies in analogy with liquid EAN. Proton fluctuations, which disturb the crystal nucleation of liquid pILs at room temperature, cause multiple crystal pathways via a non-equilibrium state.
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