Temperature- and Pressure-Induced Structural Changes of Cobalt(II) in a Phosphonium-Based Ionic Liquid

McCourt, Éadaoin; Wojnarowska, Ż.; Jacquemin, Johan; Nockemann, Peter; Manyar, Haresh; Hawełek, ᴌ.; Paluch, Marian

doi:10.1021/acs.jpcc.6b01325

Cited by 11 publications

(9 citation statements)

References 28 publications

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“…In this context, ionic liquids (ILs) present a viable alternative to ligating solvents with their high thermal stability and desirable structure tunability, , allowing their application in different fields. − Moreover, the associated anions in ILs can be chosen to adjust coordination capability toward metal ions. In this regard, imidazolium-based ILs have been used in combination with Ni(II) salts, both in solutions and thin films, to obtain systems that show a thermochromic transition from green to blue in the temperature range 35–65 °C or room temperature–120 °C. − Furthermore, imidazolium ILs have also been used in combination with Co(II) salts, giving systems in which the thermochromic switch occurs under room − or subzero temperatures or alternatively, at very high temperatures. − These transition temperatures limit the use such IL–metal complexes within the solar thermal energy range. To overcome such limitations, we have recently introduced a self-contained IL–Co(II) system, where the ILs were synthesized from a sugar-based source (derived from food waste), utilizing a simple reaction scheme.…”

Section: Introductionmentioning

confidence: 99%

Ionic Liquids–Cobalt(II) Thermochromic Complexes: How the Structure Tunability Affects “Self-Contained” Systems

Billeci

Gunaratne

Licence

et al. 2021

ACS Sustainable Chem. Eng.

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With the aim of obtaining thermochromic systems with potential applications in solar energy storage, we evaluated the behavior of some sugar-based ionic liquids (ILs)−Co(NTf 2 ) 2 complexes, in IL solution, as a function of temperature. Different structural changes on the cation, the nature of the anion, and the nature of the IL used as the solvent were considered. The analysis of the above factors was carried out through a combined approach of different techniques, that is, variable temperature UV−vis and NMR spectroscopies, conductivity, and thermal gravimetric analysis. The thermochromic systems were analyzed both as solutions and as thin films, and the data collected highlight the defining role played by both the cation structure and the solvent nature in determining their performance. Most of the investigated systems show a chromogenic transition from pink to blue, occurring in a temperature range suitable for practical applications (40−60 °C). Interestingly, when embedded in a polymeric matrix, thin films with high recyclability and long life are also described.

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Section: Introductionmentioning

confidence: 99%

Ionic Liquids–Cobalt(II) Thermochromic Complexes: How the Structure Tunability Affects “Self-Contained” Systems

Billeci

Gunaratne

Licence

et al. 2021

ACS Sustainable Chem. Eng.

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“…We, thus, suggest that, in accordance with equation 10, 4) is present in a tetrahedral geometry and becomes octahedral when one dicyanamide anion is added in order to form[Co(NT 2 ) (3− ) ( ) 4 ] ( −5) .This assumption is strengthen by recent papers dealing with the geometry of cobalt(II) complexes with thiocyanate anions in ionic liquid media. [43,44] In this work tetrahedral complexes exhibit a strong blue colour while a bright red colour is observed for octahedral complexes.…”

Section: Speciation Of Co(ii) In [C1c4pyrr][ntf2]mentioning

confidence: 59%

Dicyanamide Ions as Complexing Agents of Co(II): From Weak Ligands in Water to Strong Ones in an Ionic Liquid

Gras

Papaïconomou

Chaînet

et al. 2018

Solvent Extraction and Ion Exchange

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The complexation of cobalt cations (Co(II)) by dicyanamide (DCA-) in water and 1-butyl-1methylpyrrolidiniumbis(trifluoromethanesulfonyl)imide ([C1C4Pyrr][NTf2]) has been investigated by recording UV-vis spectra at 20 °C for solutions containing different ratios for the concentrations of DCAvs. Co(II) (R = [DCA-]/[Co(II)]). The variation of the absorbance at a fixed wavelength as a function of R was expressed using the Beer Lambert law, based on a chemical model assuming the formation of up to four successive cobalt-dicyanamide complexes. This allowed us to determine the speciation of cobalt and the complexation constants of all complexes in both aqueous and ionic liquid media. In water, a unique complex of [Co(H2O)5(DCA)] + exhibiting a weak complexation constant (K = 20.5) is observed. In the ionic liquid, cobalt is shown to coordinate with up to four dicyanamide anions. All species coexist until the ratio R reaches 5000 where more than 90 % of the fourth and last complex [Co(NTf2)(3-x)(DCA)4] (x-5) is formed.In addition, the extraction of cobalt towards hydrophobic ionic liquids trihexyltetradecylphosphonium dicyanamide ([P66614][DCA]) and trihexyltetradecylphosphonium bis(trifluoromethanesulfonyl)imide ([P66614][NTf2]) was carried out using various concentration of DCA both in the aqueous and ionic liquid phases. Results were found to correlate very well with the speciation of Co(II) obtained in this work.

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“…This fact is due to a larger number of cations and anions per volume when higher concentrations are used. Moreover, at constant concentration, conductivity increases slightly when temperature is raised [26,37,39,51]; on the other hand, conductivity decreases with the dilution of MILs in aqueous solution [58]. This behavior may be explained due to reduced viscosity at higher temperature that allows faster cation and anion movement within the solution [26].…”

Section: Conductivitymentioning

confidence: 99%

An overview of magnetic ionic liquids: From synthetic strategies to applications in microextraction techniques

Alves

Neto

Scheid

et al. 2021

J of Separation Science

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Remarkable progress has been achieved in the application of magnetic ionic liquids in microextraction-based procedures. These materials exhibit unique physicochemical properties of ionic liquids featuring additional responses to magnetic fields by incorporating a paramagnetic component within the chemical structure. This intriguing property can open new horizons in analytical extractions because the solvent manipulation is facilitated. Moreover, the tunable chemical structures of magnetic ionic liquids also allow for task-specific extractions that can significantly increase the method selectivity. This review aimed at providing an up-to-date overview of articles involving synthesis, physicochemical properties, and applications of magnetic ionic liquids highlighting recent developments and configurations. Moreover, a section containing critical evaluation and future trends in magnetic ionic liquid-based extractions is included.

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Temperature- and Pressure-Induced Structural Changes of Cobalt(II) in a Phosphonium-Based Ionic Liquid

Cited by 11 publications

References 28 publications

Ionic Liquids–Cobalt(II) Thermochromic Complexes: How the Structure Tunability Affects “Self-Contained” Systems

Ionic Liquids–Cobalt(II) Thermochromic Complexes: How the Structure Tunability Affects “Self-Contained” Systems

Dicyanamide Ions as Complexing Agents of Co(II): From Weak Ligands in Water to Strong Ones in an Ionic Liquid

An overview of magnetic ionic liquids: From synthetic strategies to applications in microextraction techniques

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