While ionic liquids
have proved to be versatile materials for a
wide spectrum of applications, e.g., energy, materials, and medicine,
several challenges remain concerning the rational design of novel
materials. In light of this, a series of four triphenylphosphonium-based
ionic liquids have been synthesized for the first time. These compounds
exhibit high thermal stability with decomposition temperatures up
to 450 °C. Their solid-state structures are characterized by
single-crystal X-ray diffraction and the intermolecular interactions
rigorously analyzed via Hirshfeld surface analysis. It was found
that the unique geometries of the anions used in the study form distinct
interactions with the cations. The interactions in the crystalline
state are correlated with the thermal properties of the four ionic
liquids to rationalize the melting points and phase transitions for
each compound. The observed arrangements of the alkyl chains on the
cations are investigated computationally to gain an understanding
of how rotational freedom may impact the thermal properties of the
compounds. By intention, each IL reported in this work offers a unique
property profile and contributes to the ever-growing ionic liquid
catalog.
A heteroaryl sulfonyl(VI) fluoride, 4‐chloro‐7‐fluorosulfonyl‐2,1,3‐benzoxadiazole, was synthesized from its chloride counterpart (4‐chloro‐7‐chlorosulfonyl‐2,1,3‐benzoxadiazole) and the X‐ray structure analysis of these compounds and the interactions in the solid‐state were thoroughly examined. Hirshfeld surface analysis is used to provide a thorough and complete picture of the changes arising from the different halides in the functional groups. Surface analysis reveals that the fluoride does not participate in any hydrogen interactions as opposed to the chloride. However, the fluorine atom is observed to form close interactions with several π bonds. For both moieties, however, the sulfonyl oxygens show comparable interactions with respect to both magnitude and interatomic distances. The Hirshfeld surface analysis is coupled with computational studies to help elucidate the observed interactions that are found from the distinct nitrogen, chlorine, and oxygen atoms present in the molecules, providing new physical insights to the correlation between their structures and properties
Two crystals incorporating the thiamine·HCl cation and the fluorinated anion 1,3-disulfonylhexafluoropropyleneimide have been characterized via single-crystal X-ray diffraction. The host-guest interactions of thiamine with the anions are analyzed and characterized using Hirshfeld surface analysis. The cations in both structures form a dimer in the solid-state via reciprocal hydrogen bonding through the amine and hydroxyl moieties. Additional investigation into the interactions responsible for dimer formation found that the sulfur atom in the thiazolium ring interacting with several hydrogen atoms to form stabilizing interactions. These interactions in the dimer are further analyzed using reduced density gradient analysis and the results are correlated to the fingerprint plots derived from the Hirshfeld surfaces. Moreover, specific interactions are observed from the cyclical anions, with both the fluorine and sulfonyl oxygen atoms participating in bridging interactions, displaying the diverse host-guest properties of thiamine.
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