ABSTRACT
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- (= (FSO2)2N-) 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 (CF3BF3- and PF6-) displayed a rotator phase rather than the IPC phase. In these cases, the coordination numbers were six at low temperatures.
ABSTRACT
Owing to their high ionic conductivity and negligible vapor pressure, ionic liquids (ILs) find applications in various electronic devices. However, fabricating IL-based photocontrollable devices remains a challenge. In this study, we developed organometallic ILs with reversible light- and heat-controlled ionic conductivities for potential use in tunable devices. The physical properties and stimulus responses of ILs containing a cationic sandwich Ru complex with two coordinating substituents were investigated. UV photoirradiation of these ILs triggered cation photodissociation, resulting in their transformation into viscoelastic coordination polymers wherein the coordinating substituents bridged the Ru centers. Owing to the anion coordination, salts with coordinating anions such as CF3SO2NCN-, B(CN)4-, and BF2(CN)2- exhibited faster response and higher conversion than those with noncoordinating anions including (FSO2)2N- and (CF3SO2)2N-. All photoproducts reverted to their original ILs upon heating, except for the photoproduct of the BF2(CN)2 salt, which decomposed upon heating. Light- and heat-induced reversible changes occur in most cases between the high-ionic-conductive IL state and low-ionic-conductive coordination polymer state. Unlike previously reported ILs with three or one cation substituent, the current ILs exhibited both high reactivity and large ionic conductivity changes.
ABSTRACT
OBJECTIVE: Temporally extended signal space separation (tSSS) is a powerful method for artifact suppression in magnetoencephalography (MEG). Because tSSS first separates MEG signals coming from inside and outside a certain sphere, definition of the sphere origin is important. For this study, we explored the influence of origin choice on tSSS performance in spontaneous and evoked activity from epilepsy patients. METHODS: Interictal epileptiform discharges (IEDs) and somatosensory evoked fields (SEFs) were processed with two tSSSs: one with the default origin of (0, 0, 40 mm) in the head coordinate, and the other with an individual origin estimated using each patient's anatomical magnetic resonance imaging (MRI). Equivalent current dipoles (ECDs) were calculated for the data. The ECD location and quality of estimation were compared across conditions. RESULTS: MEG data from 21 patients revealed marginal differences in ECD location, but the estimation quality inferred from goodness of fit (GOF) and confidence volume (CV) was better for the tSSS with individual origins. This choice affected IEDs more than it affected SEFs. CONCLUSIONS: Individual sphere model resulted in better GOF and CV. SIGNIFICANCE: Application of tSSS using an individual origin would be more desirable when available. This parameter might influence spontaneous activity more strongly.
Subject(s)
Epilepsy , Evoked Potentials, Somatosensory , Magnetoencephalography , Humans , Magnetoencephalography/methods , Male , Female , Adult , Epilepsy/physiopathology , Epilepsy/diagnostic imaging , Evoked Potentials, Somatosensory/physiology , Young Adult , Middle Aged , Artifacts , Magnetic Resonance Imaging/methods , Adolescent , Brain/physiopathology , Brain/diagnostic imagingABSTRACT
We synthesized several protic ionic liquids (ILs) composed of onium cations and the (trifluoromethylsulfonyl)(vinylsulfonyl)amide anion. The addition of a base catalytically facilitated their transformation into zwitterions (ZIs) under solvent-free conditions, which is a convenient method for synthesizing ZIs from ILs.
ABSTRACT
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.
ABSTRACT
Cationic rhodium complexes with 1,5-cyclooctadiene (cod) ligands are important organometallic compounds that are useful as precatalysts; however, their solid-state structures and thermal properties have not been adequately investigated. In this study, we synthesized [Rh(cod)L]X (L = cod, C6H6, PhMe; X = SbF6, (FSO2)2N (= FSA), CF3BF3, CB11H12) and investigated their phase behaviors, crystal structures, and reactivities. The phase transitions of these salts result in disordered solid-state structures. Moreover, the structural disorder increases with a decrease in the cation symmetry in the SbF6 salts; [Rh(cod)(PhMe)]SbF6 exhibits a rotator phase, and the cations in other salts exhibit a dynamic rotational disorder. In contrast, a lower crystal symmetry with less cation disorder is observed for FSA salts. The thermal stabilities and reactivities of these salts were further investigated. FSA salts with arene ligands produce anion-coordinated complexes upon melting, and SbF6 salts with arene ligands produce [Rh(cod)L'2]SbF6 (L' = MeCN and SMe2) via an in situ single-crystal-to-single-crystal ligand-exchange reaction.
ABSTRACT
Several meltable coordination polymers (CPs) that possess substantial advantages attributable to their high flexibility and processability have been developed recently; however, the melting mechanism and vitrification conditions of these materials are not yet fully understood. In this study, we synthesized meltable CPs [A][K(TCM)2] (A = onium cation, TCM = C(CN)3-) incorporating ionic liquid components and investigated their crystal structures and melting behaviors in detail. These CPs feature two- or three-dimensional anionic [K(TCM)2]n- frameworks incorporating onium cations. Each CP was found to undergo incongruent melting at a temperature between 73 and 192 °C to produce a heterogeneous mixture of the ionic liquid ([A][TCM]) and microcrystalline K[TCM]. Furthermore, they formed homogeneous liquids upon further heating to â¼240 °C. The melting points of these CPs were linearly correlated with those of their constituent ionic liquids. The vitrification of these materials upon rapid cooling from the molten state was further investigated. The cooling rates required for vitrification differed greatly between the CPs and were correlated with the cation flexibility.
ABSTRACT
Ionic liquids (ILs) containing cationic mixed-valence biferrocenylene derivatives were synthesized with an octanoyl or octyl substituent in each cation. Their melting points ranged between 25 and 39 °C, and the octanoyl derivatives exhibited higher melting points than the octyl derivatives. In addition, each IL exhibited a glass transition in the temperature ranging from -66 to -45 °C after melting. Their melting points were â¼10 °C higher than those of mononuclear octamethylferrocenium salts bearing the same substituents. The solvent polarity (ETN) and Kamlet-Taft parameters (π*, α, and ß) of these dinuclear and mononuclear ILs were then examined. The dinuclear ILs bearing octanoyl substituents exhibited significant increases in ETN and π* and a decrease in α with the decreasing temperature, whereas the other ILs exhibited a significantly less pronounced temperature dependence. Finally, the intervalence charge-transfer (or charge-resonance) bands of the octanoyl dinuclear ILs exhibited red shifts with the decreasing temperature, which can be regarded as self-thermosolvatochromism.
ABSTRACT
An ionic-liquid-containing 2D coordination polymer was synthesized via a solvent-free reaction. The material exhibited incongruent melting at 112 °C, forming a solid-liquid mixture; further heating to 240 °C led to complete melting. Upon cooling, the melt transformed into a solid-liquid mixture, from which the coordination polymer was gradually recovered at ambient temperature. Rapid cooling (>200 °C s-1) of the melt resulted in complete vitrification at -28 °C.
ABSTRACT
The reversible formation of ionic liquid gels, or ionogels, upon external stimuli could improve their versatility and expand their application scope in electronic, biomedical, and micro-engineering systems. Herein, we developed organometallic compounds that release low-molecular-weight gelators upon photoirradiation, which facilitate the on-demand photogelation of ionic liquids (ILs). The chemical formulae of the gelator-coordinated complexes are [Ru(C5H5)L]X (L = C6H5NHCONHC12H25; X = PF6, B(CN)4). Each of the complexes were ILs that are easy to synthesize and miscible in ILs. By adding a small amount of the complex, various ILs were transformed to gels upon UV photoirradiation. The PF6 salt allowed the photogelation of ILs with coordinating substituents, whereas the B(CN)4 salt allowed the photogelation of non-coordinating ILs, albeit the reaction was slower. These gels underwent the reverse reaction and liquefied back when heated, and the photogelation was repeatable for ILs with coordinating cations.
ABSTRACT
The bis(trifluoromethanesulfonyl)amide anion (Tf2N), which is a common component of ionic liquids, often exhibits disorder in the solid state. In this study, the phase transitions and crystal structures of the Tf2N salts of 1,1â´-dineopentyl-1',1â³-biferrocene (=npBifc), 1',1â³-biferrocene (=Bifc), ferrocene, and cobaltocene (1-4, respectively) were compared. All the salts exhibited phase transitions at low temperatures, which are accompanied by anion ordering, though the ordering was not complete in 2 and 3. X-ray crystallographic investigation revealed that the cations and anions in 1 and 2 adopted alternating arrangements and segregated columnar arrangements, respectively. The cation in 1 exhibited a symmetrical, average-valence structure in the room-temperature phase owing to rapid valence tautomerization, whereas the cation exhibited an unsymmetrical structure in the low-temperature phase. The cation in 2 exhibited an unsymmetrical, trapped-valence structure in both phases. The cation valence states in these salts were accounted for by the electrostatic interactions between the cations and anions. The crystal structures and phase behavior of the ferrocenium salt 3 were very different from those of 4.
ABSTRACT
The temperature dependence of magnetic susceptibility of [FeIII(azp)(qsal-Me)]·0.5CH3OH [Hqsal-Me = 5-methyl-N-(8-quinoyl)salicylaldimine, H2azp = 2,2'-azobisphenol] demonstrated that the spin-crossover (SCO) transition behavior changed from an abrupt transition to consecutive gradual conversions, and moreover, the initial abrupt transition was recovered, keeping the complex at room temperature. The variable-temperature crystal structures revealed that an SCO-triggered linkage isomerization of the azobenzene ligand from one orientation to two disordered orientations and the relaxation from the disordered orientations to the original orientation occurred. The high-spin to low-spin relaxation kinetics and theoretical calculation indicate that the pedal-like motion of the azobenzene ligand can be on in the high-spin state whereas off in the low-spin state.
ABSTRACT
Metal complexes with thiocyanate (SCN-) ligands typically exhibit S- or N-coordinated linkage isomers. In this study, to explore ionic liquids that exhibit stimuli-responsiveness based on linkage isomerization, we synthesized an ionic liquid containing a cationic half-sandwich thiocyanate complex, [Ru(C6H6)(NCS)L]Tf2N (L = N-hexyl-2-pyridinemethanimine, Tf2N = bis(trifluoromethanesulfonyl)amide anion). The as-synthesized ionic liquid was a 0.7:0.3 mixture of N- and S-coordinated isomers, presenting as an extremely viscous liquid exhibiting a glass transition at 0 °C. Isomerization from the N- to the S-coordinated isomer occurred upon UV photoirradiation or heating, although thermal isomerization was accompanied by significant decomposition. The N- and S-coordinated isomers were separated into brown and orange liquids, respectively, using gel permeation chromatography. Each isomer exhibited a small solvatochromic absorption shift in organic solvents, with different solvent dependences observed for the two isomers.
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 salts have the general chemical formula [Ru(C5H5)(C6H5CHCH3OCH3)]X (X = CB11H12, CF3BF3, PF6, CPFSA (= [double bond, length as m-dash]CF2(SO2CF2)2N)), where the ruthenium complex possesses a chiral substituent. The racemates of the salts with the CB11H12, CF3BF3, and PF6 anions crystallized as a solid solution, racemic compound, and conglomerate, respectively. The (S)-enantiomer and the racemate of the CB11H12 salt exhibited phase transitions to the ionic plastic phase and melted at high temperatures. Further, this salt exhibited polymorphism, as crystallographically investigated. Most of the other salts were ionic liquids exhibiting no plastic phase. The CPFSA salt was liquid and exhibited glass transition at low temperatures.
ABSTRACT
The reversible switching of bonding modes in coordination polymers through the application of external stimuli leads to versatile mechanical and electronic functions. However, the exploration of such a system remains a great challenge. In this study, we designed liquid mixtures comprising a photoreactive organometallic ionic liquid and a bridging ligand, which form intermolecular coordination bonds upon photoirradiation. The liquid mixture of an ionic liquid [Ru(C5H5){Ph(CH2)3CN}][(SO2F)2N] (1) and a tridentate ligand N(C2H4CN)3 was transformed into an elastomer of an amorphous coordination polymer upon ultraviolet photoirradiation. By contrast, the photoirradiation of the mixture of 1 and a bidentate ligand NC(CH2)4CN produced a highly viscous liquid comprising coordination-bonded oligomers. In these reactions, photoirradiation causes dissociation of the organometallic cation, followed by the formation of intermolecular coordination bonds via the bridging ligands. The photoproducts underwent reverse reactions thermally. Based on coordination transformation, the ionic conductivity and viscoelasticity of these materials were reversibly controlled by the application of light and heat.
ABSTRACT
A neutral heteroleptic Fe(III) complex 1 derived from a π-extension of the parent complex 2 was prepared and characterized. Complex 1 exhibited an abrupt spin crossover (SCO) transition exactly at room temperature (TSCO = 298 K). A crystal structure analysis of 1 revealed that the Fe(III) complex molecules formed a three-dimensional π-stacking interaction network. To thermodynamically clarify the mechanism of the SCO transition, the thermodynamic parameters of the SCO transitions for 1 and 2 were deduced from the temperature dependence of the magnetic susceptibility in the solid and solution states using the regular solution model. A comparison of the SCO enthalpy difference between the solid and molecule for 1 and 2 revealed that the lattice enthalpy difference would largely contribute to the SCO transition enthalpy difference. A computational evaluation of intermolecular interactions and lattice energies before and after the SCO transitions in 1 and 2 disclosed the significant contribution of the next-nearest neighbor dispersion interactions to the lattice enthalpy differences. This finding indicates that not only conventional nearest neighbor intermolecular interactions but also next-nearest neighbor dispersion interactions should be taken into account to understand the fundamental mechanism of a phase transition in molecular solids.
ABSTRACT
Ru-containing ionic liquids [Ru(C5H5){C6H3(OC6H12CN)3}][N(SO2F)2] (1) and [Ru(C5H5){C6H5(OC3H6CN)}][N(SO2F)2] (2), having different numbers of substituents, were reversibly converted to coordination polymer solids and oligomeric liquids, respectively, by UV photoirradiation and heating. This feature enabled the control of their ionic conductivities and viscoelastic properties.
ABSTRACT
To explore the structural transformation of cyclopentadienyl ruthenium (CpRu) complexes in response to external stimuli, the reaction of [RuCp(MeCN)3][X] (X = PF6, (FSO2)2N [= FSA]) and tris(alkylthio)benzenes (1,3,5-C6H3(SR)3; L 1 : R = Pr, L 2 : R = Me) was investigated, and the crystal structures and thermal properties of the products were examined. The reaction produced the sandwich complexes [RuCpL n ][X] or dinuclear complexes [Ru2Cp2(µ-L n )2(CH3CN) m ][X]2 (X = PF6, FSA) depending on the reaction conditions. The sandwich complex [RuCpL 1 ][FSA] was an ionic liquid. The solids of dinuclear complexes transformed into the thermodynamically stable sandwich complexes upon heating accompanied by acetonitrile loss. This change resulted in a transformation from crystal to ionic liquid for complexes with the FSA anion. UV irradiation of the sandwich complex [RuCpL 1 ][PF6] in methanol produced the dinuclear complex [Ru2Cp2(µ-L 1 )2 L 1 2][PF6]2. The complex transformed into the sandwich complex upon heating.
ABSTRACT
Although the coordination chemistry of rhenium complexes is a rapidly expanding research field, little is known about their thermal properties. In this study, we synthesized several rhenium tricarbonyl complexes with tridentate ligands (L) having S or N as donor atoms, fac-[Re(CO)3L]X (X = Tf2N [= bis(trifluoromethanesulfonyl)amide)], PF6) and fac-[Re(CO)3LCl], and investigated their thermal properties and crystal structures. The Tf2N salts were room temperature ionic liquids. The S-coordinated complexes, having longer coordination bonds, were less thermally stable than the N-coordinated complexes. Even though fac-[Re(CO)3LCl] are bidentate coordination complexes, they were thermally more stable than the isomeric tridentate complexes fac-[Re(CO)3L]Cl.
ABSTRACT
The PdII catalyzed carbonylation of allenyl ketones has been investigated. Carbonylative dimerization predominantly proceeded to afford bis(3-furanyl)methanones 2 as the major products. The use of DMSO strikingly changed the course of the reaction, affording methyl 3-furancarboxylates 3 as the major products. DFT calculations revealed that DMSO stabilized the methanol-coordinated intermediate, leading to methoxycarbonylation. Substituted furans 2 and 3 were selectively synthesized from the same allenyl ketone substrate.