Abstract
(3-Nitroanilinium) (18-crown) (PF6) (1), which is an organic-inorganic hybrid containing one-dimensional chains of hydrogen-bonded supramolecular cations, was synthesized under slow evaporation conditions and subjected to differential scanning calorimetry, temperature-dependent dielectric measurements, and variable-temperature single-crystal X-ray diffraction analysis. These analyses revealed the occurrence of a reversible structural phase transition [P21/n P21/c] at 223 K and a dielectric anomaly, which, based on the results of structural analysis and potential energy calculations, was attributed to the synergistic effect between the pendulum-like motion of the nitro group in the supramolecular cation, (3-nitroanilinium)(18-crown), and the order-disorder motion of PF6− anions.
Highlights
Supramolecular assemblies constructed from inorganic and organic building blocks have become important for the fields of host-guest chemistry and the theoretical modeling of structure-property relationships [1,2,3,4,5]
IR spectroscopy confirmed the presence of three components (18-crown-6, 3-nitroanilinium cation, and PF6 − anion) in crystalline 1
1 was concluded to be stable at temperatures below its melting point and was characterized by differential scanning calorimetry (DSC), as this technique can effectively detect reversible phase transitions occurring upon heating and cooling
Summary
Supramolecular assemblies constructed from inorganic and organic building blocks (ionic or molecular) have become important for the fields of host-guest chemistry and the theoretical modeling of structure-property relationships [1,2,3,4,5]. Novel organic-inorganic hybrid complexes have the potential of combining the distinct properties of their components and, exhibit appealing features (e.g., dielectric anisotropy, uniaxial polarity ferroelectricity, and strongly non-linear properties) and diverse structures (e.g., zero-dimensional molecular motors, one-dimensional chains, two-dimensional layers, and three-dimensional networks) [6,7,8,9,10]. Crown ethers containing repeating –OCH2 CH2 O– units exhibit high flexibility, i.e., can adopt different shapes [17,18,19,20,21,22,23]. The combination of 18-crown-6 with Ar–NH3 + guests in a 1:1 stoichiometry affords [(Ar–NH3 )·(18-crown-6)]+ supramolecular cation units in which the Ar–NH3 +
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