Effect of substituents and anions on the phase behavior of Ru(ii) sandwich complexes: exploring the boundaries between ionic liquids and ionic plastic crystals

Literature Information

Publication Date 2017-01-17
DOI 10.1039/C6CP08308K
Impact Factor 3.676
Authors

Takumi Tominaga, Takahiro Ueda, Tomoyuki Mochida


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Abstract

We recently developed ionic liquids containing cationic sandwich complexes. However, salts of the sandwich complexes often exhibit ionic plastic phases with high melting points. To explore the boundaries between ionic liquids and plastic crystals of sandwich salts, we investigated, in detail, the phase behavior of ruthenium complexes [Ru(C5H5)(C6H5R)][X] ([C0][X]: R = H, [C1][X]: R = Me, [C2][X]: R = Et, [C4][X]: R = Bu). Among salts containing the anions PF6−, FSA−, and B(CN)4−, [C0][X] and [C1][X] are solids that exhibit plastic phases at or above room temperature, whereas [C2][X] and [C4][X] are mostly ionic liquids. Salts containing the C(CN)3− anion exhibited lower melting points than the other salts. X-ray crystallography reveals that the cations and anions in most of these salts are arranged alternately in the solid state. However, in the case of [C0][C(CN)3], the cations and anions are stacked independently, thereby providing weaker cation–anion interactions that account for the relatively low melting point of this salt.

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DOI: 10.1039/C4CP90060J

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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