skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis and characterization of low viscosity hexafluoroacetylacetonate-based hydrophobic magnetic ionic liquids

Abstract

Magnetic ionic liquids (MILs) are distinguished from traditional ionic liquids (ILs) by the incorporation of a paramagnetic component within their chemical structure. Hydrophobic MILs are novel solvents that can be used in many applications, including liquid–liquid extraction (LLE) and catalysis. Low viscosity and low water solubility are essential features that determine their feasibility in LLE. Here, we synthesized extremely hydrophobic MILs by using transition and rare earth metal hexafluoroacetylacetonate chelated anions paired with the trihexyl(tetradecyl)phosphonium ([P 66614 +]) cation. Hydrophobic MILs exhibiting water solubilities less than 0.01% (v/v) were synthesized in a rapid two-step procedure. Furthermore, the viscosities of the MILs are among some of the lowest ever reported for hydrophobic MILs (276.5–927.9 centipoise (cP) at 23.7 °C) dramatically improving the ease of handling these liquids. For the first time, the magnetic properties of MILs possessing hexafluoroacetylacetonate chelated metal anions synthesized in this study are reported using a superconducting quantum interference device (SQUID) magnetometer. We also achieved an effective magnetic moments (μ eff) as high as 9.7 and 7.7 Bohr magnetons (μ B) by incorporating high spin dysprosium and gadolinium ions, respectively, into the anion component of the MIL. The low viscosity, high hydrophobicity, and large magnetic susceptibility of thesemore » MILs make them highly attractive and promising solvents for separations and purification, liquid electrochromic materials, catalytic studies, as well as microfluidic applications.« less

Authors:
 [1];  [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
  2. Ames Lab. and Iowa State Univ., Ames, IA (United States). Division of Materials Science adn Engineering
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1371896
Report Number(s):
IS-J 9373
Journal ID: ISSN 1144-0546; NJCHE5
DOE Contract Number:  
AC02-07CH11358; CHE-1413199
Resource Type:
Journal Article
Journal Name:
New Journal of Chemistry
Additional Journal Information:
Journal Volume: 41; Journal Issue: 13; Journal ID: ISSN 1144-0546
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Pierson, Stephen A., Nacham, Omprakash, Clark, Kevin D., Nan, He, Mudryk, Yaroslav, and Anderson, Jared L. Synthesis and characterization of low viscosity hexafluoroacetylacetonate-based hydrophobic magnetic ionic liquids. United States: N. p., 2017. Web. doi:10.1039/c7nj00206h.
Pierson, Stephen A., Nacham, Omprakash, Clark, Kevin D., Nan, He, Mudryk, Yaroslav, & Anderson, Jared L. Synthesis and characterization of low viscosity hexafluoroacetylacetonate-based hydrophobic magnetic ionic liquids. United States. doi:10.1039/c7nj00206h.
Pierson, Stephen A., Nacham, Omprakash, Clark, Kevin D., Nan, He, Mudryk, Yaroslav, and Anderson, Jared L. Thu . "Synthesis and characterization of low viscosity hexafluoroacetylacetonate-based hydrophobic magnetic ionic liquids". United States. doi:10.1039/c7nj00206h.
@article{osti_1371896,
title = {Synthesis and characterization of low viscosity hexafluoroacetylacetonate-based hydrophobic magnetic ionic liquids},
author = {Pierson, Stephen A. and Nacham, Omprakash and Clark, Kevin D. and Nan, He and Mudryk, Yaroslav and Anderson, Jared L.},
abstractNote = {Magnetic ionic liquids (MILs) are distinguished from traditional ionic liquids (ILs) by the incorporation of a paramagnetic component within their chemical structure. Hydrophobic MILs are novel solvents that can be used in many applications, including liquid–liquid extraction (LLE) and catalysis. Low viscosity and low water solubility are essential features that determine their feasibility in LLE. Here, we synthesized extremely hydrophobic MILs by using transition and rare earth metal hexafluoroacetylacetonate chelated anions paired with the trihexyl(tetradecyl)phosphonium ([P66614+]) cation. Hydrophobic MILs exhibiting water solubilities less than 0.01% (v/v) were synthesized in a rapid two-step procedure. Furthermore, the viscosities of the MILs are among some of the lowest ever reported for hydrophobic MILs (276.5–927.9 centipoise (cP) at 23.7 °C) dramatically improving the ease of handling these liquids. For the first time, the magnetic properties of MILs possessing hexafluoroacetylacetonate chelated metal anions synthesized in this study are reported using a superconducting quantum interference device (SQUID) magnetometer. We also achieved an effective magnetic moments (μeff) as high as 9.7 and 7.7 Bohr magnetons (μB) by incorporating high spin dysprosium and gadolinium ions, respectively, into the anion component of the MIL. The low viscosity, high hydrophobicity, and large magnetic susceptibility of these MILs make them highly attractive and promising solvents for separations and purification, liquid electrochromic materials, catalytic studies, as well as microfluidic applications.},
doi = {10.1039/c7nj00206h},
journal = {New Journal of Chemistry},
issn = {1144-0546},
number = 13,
volume = 41,
place = {United States},
year = {2017},
month = {5}
}

Works referenced in this record:

Synthesis and characterization of Magnetic Ionic Liquids (MILs) for CO 2 separation
journal, May 2014

  • Santos, Esther; Albo, Jonathan; Rosatella, Andreia
  • Journal of Chemical Technology & Biotechnology, Vol. 89, Issue 6
  • DOI: 10.1002/jctb.4323

Room-Temperature Ionic Liquids: Solvents for Synthesis and Catalysis. 2
journal, May 2011

  • Hallett, Jason P.; Welton, Tom
  • Chemical Reviews, Vol. 111, Issue 5
  • DOI: 10.1021/cr1003248

Structural disorder and magnetism in rare-earth (R) R117Co54+xSn112±y
journal, April 2013


Fe-containing magnetic ionic liquid as an effective catalyst for the glycolysis of poly(ethylene terephthalate)
journal, March 2010


Ionic Liquids Based on FeCl 3 and FeCl 2 . Raman Scattering and ab Initio Calculations
journal, May 2001

  • Sitze, Melissa S.; Schreiter, Eric R.; Patterson, Eric V.
  • Inorganic Chemistry, Vol. 40, Issue 10
  • DOI: 10.1021/ic001042r

Extraction of DNA by Magnetic Ionic Liquids: Tunable Solvents for Rapid and Selective DNA Analysis
journal, January 2015

  • Clark, Kevin D.; Nacham, Omprakash; Yu, Honglian
  • Analytical Chemistry, Vol. 87, Issue 3
  • DOI: 10.1021/ac504260t

Air and water stable ionic liquids in physical chemistry
journal, January 2006

  • Endres, Frank; Zein El Abedin, Sherif
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 18
  • DOI: 10.1039/b600519p

Synthesis, Structure, and Antimicrobial Activity of Cobalt(II) Complex Derived from Hexafluoroacetylacetone and N,N,N′,N′-Tetramethylethane-1,2-diamine
journal, October 2015

  • Liu, Qiao-Ru; Xue, Ling-Wei; Zhao, Gan-Qing
  • Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, Vol. 46, Issue 6
  • DOI: 10.1080/15533174.2014.989613

Trigonal-Prismatic vs. Octahedral Geometry for MnII Complexes with Innocent Didentate Ligands: A Subtle Difference as Shown by XRD and DFT on [Mn(acac)2(bpy)]
journal, June 2005

  • van Gorkum, Remy; Buda, Francesco; Kooijman, Huub
  • European Journal of Inorganic Chemistry, Vol. 2005, Issue 11
  • DOI: 10.1002/ejic.200401005

Synthetic Strategies for Tailoring the Physicochemical and Magnetic Properties of Hydrophobic Magnetic Ionic Liquids
journal, January 2015

  • Nacham, Omprakash; Clark, Kevin D.; Yu, Honglian
  • Chemistry of Materials, Vol. 27, Issue 3
  • DOI: 10.1021/cm504202v


journal, July 2005


Design of functional ionic liquids using magneto- and luminescent-active anions
journal, January 2010

  • Yoshida, Yukihiro; Saito, Gunzi
  • Phys. Chem. Chem. Phys., Vol. 12, Issue 8
  • DOI: 10.1039/B920046K

Metallocenium Ionic Liquids
journal, June 2010

  • Inagaki, Takashi; Mochida, Tomoyuki
  • Chemistry Letters, Vol. 39, Issue 6
  • DOI: 10.1246/cl.2010.572

Ionic liquids with metal chelate anions
journal, January 2012

  • Zhang, Pengfei; Gong, Yutong; Lv, Yiqi
  • Chemical Communications, Vol. 48, Issue 17
  • DOI: 10.1039/c2cc16906a

Structure and magnetic behavior of transition metal based ionic liquids
journal, January 2008

  • Del Sesto, Rico E.; McCleskey, T. Mark; Burrell, Anthony K.
  • Chem. Commun., Issue 4
  • DOI: 10.1039/B711189D

Metal−Ligand Bond Distances in First-Row Transition Metal Coordination Compounds:  Coordination Number, Oxidation State, and Specific Ligand Effects
journal, October 1998

  • See, Ronald F.; Kruse, Rebecca A.; Strub, William M.
  • Inorganic Chemistry, Vol. 37, Issue 20
  • DOI: 10.1021/ic971462p

Copper(II), cobalt(II), nickel(II) and zinc(II) complexes of Schiff base derived from benzil-2,4-dinitrophenylhydrazone with aniline
journal, July 2004

  • Raman, N.; Ravichandran, S.; Thangaraja, C.
  • Journal of Chemical Sciences, Vol. 116, Issue 4
  • DOI: 10.1007/BF02708270

Magnetic ionic liquids as PCR-compatible solvents for DNA extraction from biological samples
journal, January 2015

  • Clark, Kevin D.; Yamsek, Melissa M.; Nacham, Omprakash
  • Chemical Communications, Vol. 51, Issue 94
  • DOI: 10.1039/C5CC07253K

Paramagnetic ionic liquids for advanced applications: A review
journal, June 2016


Thermomorphic Behavior of the Ionic Liquids [C4mim][FeCl4] and [C12mim][FeCl4]
journal, December 2010


Complex Ions. IX. Magnetic Susceptibilities of Nickel and Cobalt Complex Ions from 0 to 80°
journal, July 1949

  • Field, Frank H.; Vosburgh, W. C.
  • Journal of the American Chemical Society, Vol. 71, Issue 7
  • DOI: 10.1021/ja01175a044

Thermal degradation studies of alkyl-imidazolium salts and their application in nanocomposites
journal, January 2004


Dysprosium Room-Temperature Ionic Liquids with Strong Luminescence and Response to Magnetic Fields
journal, September 2008

  • Mallick, Bert; Balke, Benjamin; Felser, Claudia
  • Angewandte Chemie International Edition, Vol. 47, Issue 40
  • DOI: 10.1002/anie.200802390

Discovery of a Magnetic Ionic Liquid [bmim]FeCl 4
journal, December 2004

  • Hayashi, Satoshi; Hamaguchi, Hiro-o
  • Chemistry Letters, Vol. 33, Issue 12
  • DOI: 10.1246/cl.2004.1590

Task-Specific Ionic Liquids
journal, September 2004


Magnetic ionic liquids: synthesis, properties and applications
journal, January 2014


Rare-Earth-Containing Magnetic Liquid Crystals
journal, May 2000

  • Binnemans, Koen; Galyametdinov, Yury G.; Van Deun, Rik
  • Journal of the American Chemical Society, Vol. 122, Issue 18
  • DOI: 10.1021/ja993351q

On the Chemical Stabilities of Ionic Liquids
journal, September 2009

  • Sowmiah, Subbiah; Srinivasadesikan, Venkatesan; Tseng, Ming-Chung
  • Molecules, Vol. 14, Issue 9
  • DOI: 10.3390/molecules14093780

Magnetic ionic liquids in analytical chemistry: A review
journal, August 2016


Solvatochromic Dyes as Solvent Polarity Indicators
journal, December 1994


Hydrophobic ionic liquids with strongly coordinating anions
journal, January 2010

  • Mehdi, Hasan; Binnemans, Koen; Van Hecke, Kristof
  • Chem. Commun., Vol. 46, Issue 2
  • DOI: 10.1039/B914977E