Thermal properties, crystal structures, and phase diagrams of ionic plastic crystals and ionic liquids containing a chiral cationic sandwich complex

Mochida, Tomoyuki; Sumitani, Ryo; Yamazoe, Tomoaki

doi:10.1039/d0cp04870d

Cited by 5 publications

(4 citation statements)

References 47 publications

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“…PCs are typically formed by ‘simple’ neutral organic molecules and, albeit having long‐range positional order, they do show mechanical plasticity [1] . After their initial discovery by Timmermans [2] in 1938, PCs have been studied by various fields, such as ferroelectrics, [3–5] magnetics [6,7] and optics [8] …”

Section: Introductionmentioning

confidence: 99%

“…PCs are typically formed by 'simple' neutral organic molecules and, albeit having long-range positional order, they do show mechanical plasticity. [1] After their initial discovery by Timmermans [2] in 1938, PCs have been studied by various fields, such as ferroelectrics, [3][4][5] magnetics [6,7] and optics. [8] Organic ionic plastic crystals (OIPCs) are considered a subclass of plastic crystals, and similarly to PCs, OIPCs possess longrange order.…”

Section: Introductionmentioning

confidence: 99%

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Non‐Globular Organic Ionic Plastic Crystal Containing a Crown‐Ether Moiety – Tuning Its Behaviour Using Sodium Salts

et al. 2022

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Organic ionic plastic crystals (OIPCs) are a class of soft materials showing positional order while still allowing orientational freedom. Due to their motional freedom in the solid state, they possess plasticity, non-flammability and high ionic conductivity. OIPC behavior is typically exhibited by 'simple' globular molecules allowing molecular rotation, whereas the interactions that govern the formation of OIPC phases in complex nonglobular molecules are less understood. To better understand these interactions, a new family of non-globular OIPCs containing a 15-crown-5 ether moiety was synthetized and character-ized. The 15C5BA molecule prepared does not exhibit the sought-after behavior because of its non-globular nature and strong intermolecular H-bonds that restrict orientational motion. However, the OIPC behavior was successfully obtained through complexation of the crown-ether moiety with sodium salts containing chaotropic anions. Those anions weaken the interactions between the molecules, allowing rotational freedom and tuning of the thermal and morphological properties of the OIPC.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Non‐Globular Organic Ionic Plastic Crystal Containing a Crown‐Ether Moiety – Tuning Its Behaviour Using Sodium Salts

et al. 2022

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“…[15d] Similarly, in the PF 6 and CF 3 BF 3 salts of 5 c, the racemate has a lower melting point than the chiral salt, where these salts formed a conglomerate and racemic compound, respectively. [19] Racemates more often form racemic compounds rather than conglomerates, and the melting point may increase or decrease in the case of racemic compounds.…”

Section: Alkyl-chain Lengthmentioning

confidence: 99%

Organometallic Ionic Liquids Containing Sandwich Complexes: Molecular Design, Physical Properties, and Chemical Reactivities

Mochida

2023

The Chemical Record

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Ionic liquids (ILs) are salts with low melting points and are useful as electrolytes and solvents. We have developed ILs containing cationic metal complexes, which form a family of functional liquids that exhibit unique physical properties and chemical reactivities originating from metal complexes. Our study explores the liquid chemistry in the field of coordination chemistry, where solid‐state chemistry is currently the main focus. This review describes the molecular design, physical properties, and reactivities of organometallic ILs containing sandwich or half‐sandwich complexes. This paper mainly covers stimuli‐responsive ILs, whose magnetic properties, solvent polarities, colors, or structures change by the application of external fields, such as light, heat, and magnetic fields, or by reaction with coordinating molecules.

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“…Some of these complexes are particularly intriguing for their magnetic properties . However, their phase transition temperatures to the IPC phase ( T c ) tend to be relatively high (e.g., 347 K for [Fe(Cp) 2 ]PF 6 ). − In our research, we synthesized various IPCs incorporating cationic sandwich complexes and evaluated their phase behaviors to elucidate the factors influencing their phase transitions (Figure a). ,− The transition temperatures of octamethylferrocenium salts ([Fe(C 5 Me 4 H) 2 ]X, where X = anion) decrease as the anion volume increases . Conversely, cobaltocenium salts ([Co(Cp) 2 ]X) and ruthenium complexes ([Ru(Cp)(arene)]X) demonstrate an opposite trend .…”

Section: Introductionmentioning

confidence: 99%

Organometallic Ionic Plastic Crystals Incorporating Cationic Half-Sandwich Complexes

Inoue,

Sumitani,

Honda

et al. 2024

Inorg. Chem.

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Ionic plastic crystals (IPCs), characterized by nearly spherical molecular ions, exhibit remarkable solid-state characteristics including high ionic conductivity. However, most IPCs are organic onium salts. Incorporating organometallic half-sandwich complexes into IPCs is challenging owing to their low-symmetry structures. This paper introduces a novel series of IPCs composed of salts derived from half-sandwich organometallic complexes. We synthesized five salts of [Ru(Cp)(tmeda)(CO)]X (tmeda = N,N,N′,N′-tetramethyl-1,2-ethanediamine, X = anion) with different anions and examined their phase behavior, crystal structures, and molecular motion in the solid-state. Salts featuring the CPFSA (= 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide), B(CN) 4 − , and FSA − (= (FSO 2 ) 2 N − ) anions underwent phase transitions to an IPC phase with a CsCl-type structure in the temperature range of 327−364 K. Employing smaller anions led to an increase in the transition temperature. In each salt, the coordination number, representing the number of anions surrounding one cation, remained eight in IPC and low-temperature phases. However, salts containing smaller anions (CF 3 BF 3 − and PF 6 − ) displayed a rotator phase rather than the IPC phase. In these cases, the coordination numbers were six at low temperatures.

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Thermal properties, crystal structures, and phase diagrams of ionic plastic crystals and ionic liquids containing a chiral cationic sandwich complex

Abstract: To investigate the effects of chirality on the phase behavior of ionic plastic crystals and ionic liquids, salts of a chiral sandwich complex with various anions were synthesized. The synthesized...

Cited by 5 publications

References 47 publications

Non‐Globular Organic Ionic Plastic Crystal Containing a Crown‐Ether Moiety – Tuning Its Behaviour Using Sodium Salts

Non‐Globular Organic Ionic Plastic Crystal Containing a Crown‐Ether Moiety – Tuning Its Behaviour Using Sodium Salts

Organometallic Ionic Liquids Containing Sandwich Complexes: Molecular Design, Physical Properties, and Chemical Reactivities

Organometallic Ionic Plastic Crystals Incorporating Cationic Half-Sandwich Complexes

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