DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Neat and Rapid Preparation of Hydrophobic Magnetic Ionic Liquids Composed of Transition Metal Chelates Featuring In-situ Formation Capabilities in Aqueous Matrices

Journal Article · · New Journal of Chemistry
DOI: https://doi.org/10.1039/d4nj00624k · OSTI ID:2325544
 [1];  [2];  [2];  [3];  [2];  [1]
  1. Ames Laboratory (AMES), Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
  2. Univ. of Alabama, Tuscaloosa, AL (United States)
  3. Ames Laboratory (AMES), Ames, IA (United States)

Magnetic ionic liquids (MILs) form a subclass of ionic liquids (ILs) that possess paramagnetic properties and can respond to an external magnetic field, facilitating ease of manipulation in immiscible solvents. Despite being popular as solvents in catalysis, organic synthesis, and separations, MILs are acquired through complex and labor-intensive synthetic/purification routes that increase cost, consume precious time, and require expertise in organic synthesis. To date, no study has successfully developed a highly simplified and easy-to-follow procedure for MIL preparation that can rapidly produce MILs and eliminate the need to purify them. In this study, transition metal-containing bis[(trifluoromethyl)sulfonyl]imide [NTf2-] salts and imidazoles, diglycolamides, and O-donor ligands were used to produce hydrophobic MILs that could maintain their chemical integrity under water for over 6 months. A neat heat/stir method was employed to form MILs for long-term storage or later use while an ¬in-situ method was used to generate the same MIL under 30 seconds in the bulk presence of water. Viscosity values as low as 198.3 cP were obtained that were comparable to previous classes of paramagnetic solvents. MILs were found to be soluble in non-polar solvents such as hexane at concentrations of up to 50% (w/v) MIL-to-solvent ratio while being insoluble in water even at 0.01% (w/v). Effective magnetic moment values for MILs ranged from 2.78 to 5.16 Bohr magnetons (µB) and were observed to be dependent on the metal center in the [NTf2-] salts. The solvents possessed excellent thermal stabilities with TODGA-based MILs exhibiting structural resilience up to 345 °C. The synthetic design of these MILs has successfully achieved the primary objective of facilitating easy access to magnetoactive solvents by reducing their preparation to a simple step consisting of mixing 2 readily available reagents to expedite production in high-throughput laboratories where these compounds can be incorporated in automated separations and analytical testing systems where their magnetic properties can be conveniently exploited.

Research Organization:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); National Science Foundation (NSF); USDOE
Grant/Contract Number:
AC02-07CH11358; CHE-2203891
OSTI ID:
2325544
Alternate ID(s):
OSTI ID: 2323281
Report Number(s):
IS-J-11,282
Journal Information:
New Journal of Chemistry, Vol. 48, Issue 15; ISSN 1144-0546
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (40)

Synthesis and characterization of Magnetic Ionic Liquids (MILs) for CO 2 separation journal May 2014
Silver-Based Deep Eutectic Solvents as Separation Media: Supported Liquid Membranes for Facilitated Olefin Transport journal July 2017
Enabling Sustainable Chemistry with Ionic Liquids and Deep Eutectic Solvents: A Fad or the Future? journal August 2022
Room-Temperature Ionic Liquids: Solvents for Synthesis and Catalysis. 2 journal May 2011
Deep Eutectic Solvents (DESs) and Their Applications journal October 2014
Carbohydrate Ionic Liquids and Salts as All-in-One Precursors for N-Doped Carbon journal November 2019
Tetraalkylphosphonium-based ionic liquids journal May 2005
Tailoring properties of natural deep eutectic solvents with water to facilitate their applications journal November 2015
A Search for Natural Hydrophobic Deep Eutectic Solvents Based on Natural Components journal January 2019
Anionic Rare-Earth Thiocyanate Complexes as Building Blocks for Low-Melting Metal-Containing Ionic Liquids journal October 2006
Magnetic ionic liquids in analytical sample preparation: A literature review journal April 2019
Magnetic deep eutectic solvents in microextraction techniques journal January 2022
Introduction: Ionic Liquids journal February 2017
Dication magnetic ionic liquids with tuneable heteroanions journal January 2013
Insights into the Synthesis and Properties of Deep Eutectic Solvents Based on Cholinium Chloride and Carboxylic Acids journal September 2014
Magnetic memory based on magnetic alignment of a paramagnetic ionic liquid near room temperature journal January 2011
High-Resolution Thermogravimetric Analysis Is Required for Evaluating the Thermal Stability of Deep Eutectic Solvents journal September 2022
Natural deep eutectic solvents as new potential media for green technology journal March 2013
Stereoselective organocatalysed reactions in deep eutectic solvents: highly tunable and biorenewable reaction media for sustainable organic synthesis journal January 2016
Synthetic Strategies for Tailoring the Physicochemical and Magnetic Properties of Hydrophobic Magnetic Ionic Liquids journal January 2015
Paramagnetic Ionic Liquids for Measurements of Density Using Magnetic Levitation journal August 2013
Influence of structural variations in 1-alkyl-3-methylimidazolium cation and tetrahalogenoferrate(iii) anion on the physical properties of the paramagnetic ionic liquids journal January 2006
Hydrophobic Deep Eutectic Solvents: A Circular Approach to Purify Water Contaminated with Ciprofloxacin journal August 2019
Magnetic Ionic Liquids in Analytical Microextraction: A Tutorial Review journal December 2022
Synthesis and characterization of magnetic ionic liquids containing multiple paramagnetic lanthanide and transition metal centers and functionalized diglycolamide ligands journal September 2022
Preparation of ternary hydrophobic magnetic deep eutectic solvents and an investigation into their physicochemical properties journal November 2022
Expanding the Potential Role of Deep Eutectic Solvents toward Facilitating the Structural and Thermal Stability of α-Chymotrypsin journal July 2020
Ultra-Low Viscosity and High Magnetic Susceptibility Magnetic Ionic Liquids Featuring Functionalized Diglycolic Acid Ester Rare-Earth and Transition Metal Chelates journal July 2023
Thermomorphic Behavior of the Ionic Liquids [C4mim][FeCl4] and [C12mim][FeCl4] journal December 2010
Designing a new type of magnetic ionic liquid: a strategy to improve the magnetic susceptibility journal January 2019
Electropolymerization of Pyrrole-Based Ionic Liquids on Selected Wireless Bipolar Electrodes journal April 2022
Deep Eutectic Solvents as Efficient Catalysts for Fixation of CO2 to Cyclic Carbonates at Ambient Temperature and Pressure through Synergetic Catalysis journal July 2021
Cobalt(ii) liquid metal salts for high current density electrodeposition of cobalt journal January 2018
Discovery of a Magnetic Ionic Liquid [bmim]FeCl 4 journal December 2004
Task-Specific Ionic Liquids journal September 2004
Dicationic Ionic Liquids as Environmentally Benign Catalysts for Biodiesel Synthesis journal December 2010
Cobalt(ii) containing liquid metal salts for electrodeposition of cobalt and electrochemical nanoparticle formation journal January 2017
Organic Synthesis in Ionic Liquids:  The Stille Coupling journal January 2001
Deep eutectic solvents in separations: Methods of preparation, polarity, and applications in extractions and capillary electrochromatography journal December 2020
Green process for production of 5-hydroxymethylfurfural from carbohydrates with high purity in deep eutectic solvents journal May 2017