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Title: Investigating the effect of ligand and cation on the properties of metal fluorinated acetylacetonate based magnetic ionic liquids

Abstract

Magnetic ionic liquids (MILs) are a subclass of ionic liquids that possess a paramagnetic metal within their chemical structure, making them susceptible to external magnetic fields. A total of twenty-four (24) MILs were prepared and characterized to investigate the effect of the ligand, cation and anion on the physiochemical properties of acetylacetonate-based MILs. It was found that thermal stabilities as high as 260 °C could be achieved by incorporating aromatic moieties in the anion structure. Additionally, the magnetic moment could be modulated by simply changing the transition metal in the anion. Magnetic moment values of 2.8 μB, 4.5 μB and 5.6 μB were obtained by using Ni(II), Co(II), and Mn(II) as the metal centers, respectively. Furthermore, the viscosity of the MILs could be tailored from a few hundred centipoise to several thousand centipoise, increasing their potential applications in numerous interdisciplinary fields. Moreover, the MILs synthesized in this study were found to be insoluble in water at a MIL-to-solvent ratio of 0.01% (w/v), making them potentially useful in targeted separations, where very hydrophobic solvents are highly desired.

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry, Iowa State University, Ames, USA
  2. Division of Materials Science and Engineering, Ames Laboratory, Iowa State University, Ames, USA
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1530898
Alternate Identifier(s):
OSTI ID: 1556104
Report Number(s):
IS-J-9988
Journal ID: ISSN 1144-0546; NJCHE5
Grant/Contract Number:  
AC02-07CH11358; CHE-1709372
Resource Type:
Published Article
Journal Name:
New Journal of Chemistry
Additional Journal Information:
Journal Name: New Journal of Chemistry Journal Volume: 43 Journal Issue: 28; Journal ID: ISSN 1144-0546
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Farooq, Muhammad Qamar, Chand, Deepak, Odugbesi, Gabriel A., Varona, Marcelino, Mudryk, Yaroslav, and Anderson, Jared L. Investigating the effect of ligand and cation on the properties of metal fluorinated acetylacetonate based magnetic ionic liquids. United Kingdom: N. p., 2019. Web. doi:10.1039/C9NJ02595B.
Farooq, Muhammad Qamar, Chand, Deepak, Odugbesi, Gabriel A., Varona, Marcelino, Mudryk, Yaroslav, & Anderson, Jared L. Investigating the effect of ligand and cation on the properties of metal fluorinated acetylacetonate based magnetic ionic liquids. United Kingdom. doi:10.1039/C9NJ02595B.
Farooq, Muhammad Qamar, Chand, Deepak, Odugbesi, Gabriel A., Varona, Marcelino, Mudryk, Yaroslav, and Anderson, Jared L. Mon . "Investigating the effect of ligand and cation on the properties of metal fluorinated acetylacetonate based magnetic ionic liquids". United Kingdom. doi:10.1039/C9NJ02595B.
@article{osti_1530898,
title = {Investigating the effect of ligand and cation on the properties of metal fluorinated acetylacetonate based magnetic ionic liquids},
author = {Farooq, Muhammad Qamar and Chand, Deepak and Odugbesi, Gabriel A. and Varona, Marcelino and Mudryk, Yaroslav and Anderson, Jared L.},
abstractNote = {Magnetic ionic liquids (MILs) are a subclass of ionic liquids that possess a paramagnetic metal within their chemical structure, making them susceptible to external magnetic fields. A total of twenty-four (24) MILs were prepared and characterized to investigate the effect of the ligand, cation and anion on the physiochemical properties of acetylacetonate-based MILs. It was found that thermal stabilities as high as 260 °C could be achieved by incorporating aromatic moieties in the anion structure. Additionally, the magnetic moment could be modulated by simply changing the transition metal in the anion. Magnetic moment values of 2.8 μB, 4.5 μB and 5.6 μB were obtained by using Ni(II), Co(II), and Mn(II) as the metal centers, respectively. Furthermore, the viscosity of the MILs could be tailored from a few hundred centipoise to several thousand centipoise, increasing their potential applications in numerous interdisciplinary fields. Moreover, the MILs synthesized in this study were found to be insoluble in water at a MIL-to-solvent ratio of 0.01% (w/v), making them potentially useful in targeted separations, where very hydrophobic solvents are highly desired.},
doi = {10.1039/C9NJ02595B},
journal = {New Journal of Chemistry},
number = 28,
volume = 43,
place = {United Kingdom},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C9NJ02595B

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Cited by: 2 works
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Works referenced in this record:

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Extractive Desulfurization Using Fe-Containing Ionic Liquids
journal, May 2008

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Dication magnetic ionic liquids with tuneable heteroanions
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A new class of magnetic fluids: bmim[FeCl/sub 4/] and nbmim[FeCl/sub 4/] ionic liquids
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Sonochemical formation of iron oxide nanoparticles in ionic liquids for magnetic liquid marble
journal, January 2012

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  • Physical Chemistry Chemical Physics, Vol. 14, Issue 15
  • DOI: 10.1039/c2cp23675c

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

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Paramagnetic Ionic Liquids for Measurements of Density Using Magnetic Levitation
journal, August 2013

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Synthetic Strategies for Tailoring the Physicochemical and Magnetic Properties of Hydrophobic Magnetic Ionic Liquids
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Design of functional ionic liquids using magneto- and luminescent-active anions
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Metallocenium Ionic Liquids
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  • DOI: 10.1246/cl.2010.572

Friedel-Crafts acylation of aromatics catalysed by supported ionic liquids
journal, July 2001


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

Synthesis and characterization of low viscosity hexafluoroacetylacetonate-based hydrophobic magnetic ionic liquids
journal, January 2017

  • Pierson, Stephen A.; Nacham, Omprakash; Clark, Kevin D.
  • New Journal of Chemistry, Vol. 41, Issue 13
  • DOI: 10.1039/C7NJ00206H

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

Faster dispersive liquid-liquid microextraction methods using magnetic ionic liquids as solvents
journal, September 2016


Dicationic ionic liquid thermal decomposition pathways
journal, January 2018

  • Patil, Rahul A.; Talebi, Mohsen; Berthod, Alain
  • Analytical and Bioanalytical Chemistry, Vol. 410, Issue 19
  • DOI: 10.1007/s00216-018-0878-0

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

Metal-Containing Ionic Liquids as Efficient Catalysts for Hydroxymethylation in Water
journal, July 2008

  • Bica, Katharina; Gaertner, Peter
  • European Journal of Organic Chemistry, Vol. 2008, Issue 20
  • DOI: 10.1002/ejoc.200800323

Evaluating the solvation properties of metal-containing ionic liquids using the solvation parameter model
journal, December 2017

  • Nan, He; Peterson, Liese; Anderson, Jared L.
  • Analytical and Bioanalytical Chemistry, Vol. 410, Issue 19
  • DOI: 10.1007/s00216-017-0802-z

Polarity study of some 1-alkyl-3-methylimidazolium ambient-temperature ionic liquids with the solvatochromic dye, Nile Red
journal, January 2000


Highly efficient extraction of phenolic compounds by use of magnetic room temperature ionic liquids for environmental remediation
journal, September 2011


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

A demonstration of crystal-field effects in octahedral complexes
journal, October 1996

  • Koubek, Edward; Elert, Mark
  • Journal of Chemical Education, Vol. 73, Issue 10
  • DOI: 10.1021/ed073p947

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

Electrochromic and magnetic ionic liquids
journal, January 2011

  • Branco, Aida; Branco, Luís C.; Pina, Fernando
  • Chem. Commun., Vol. 47, Issue 8
  • DOI: 10.1039/C0CC03892J

Preparation and evaluation of cellulose-dissolving magnetic ionic liquid
journal, June 2013


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


Solvatochromic Dyes as Solvent Polarity Indicators
journal, December 1994


Application of Iron-Containing Magnetic Ionic Liquids in Extraction Process of Coal Direct Liquefaction Residues
journal, February 2012

  • Wang, Jieli; Yao, Hongwei; Nie, Yi
  • Industrial & Engineering Chemistry Research, Vol. 51, Issue 9
  • DOI: 10.1021/ie202940k

Metal isotope effect on metal-ligand vibrations. IV. Metal complexes of acetylacetone
journal, July 1970

  • Nakamoto, Kazuo.; Udovich, Carl.; Takemoto, James.
  • Journal of the American Chemical Society, Vol. 92, Issue 13
  • DOI: 10.1021/ja00716a024

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

Using a Combination of Experimental and Computational Methods To Explore the Impact of Metal Identity and Ligand Field Strength on the Electronic Structure of Metal Ions
journal, September 2011

  • Pernicone, Naomi C.; Geri, Jacob B.; York, John T.
  • Journal of Chemical Education, Vol. 88, Issue 9
  • DOI: 10.1021/ed1010079

Discovery of a Magnetic Ionic Liquid [bmim]FeCl4.
journal, May 2005


    Works referencing / citing this record:

    Ionic Liquids for Clean Technology
    journal, April 1997


    Polarity study of some 1-alkyl-3-methylimidazolium ambient-temperature ionic liquids with the solvatochromic dye, Nile Red
    journal, January 2000


    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

    Metal-Containing Ionic Liquids as Efficient Catalysts for Hydroxymethylation in Water
    journal, July 2008

    • Bica, Katharina; Gaertner, Peter
    • European Journal of Organic Chemistry, Vol. 2008, Issue 20
    • DOI: 10.1002/ejoc.200800323

    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

    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

    Evaluating the solvation properties of metal-containing ionic liquids using the solvation parameter model
    journal, December 2017

    • Nan, He; Peterson, Liese; Anderson, Jared L.
    • Analytical and Bioanalytical Chemistry, Vol. 410, Issue 19
    • DOI: 10.1007/s00216-017-0802-z

    Dicationic ionic liquid thermal decomposition pathways
    journal, January 2018

    • Patil, Rahul A.; Talebi, Mohsen; Berthod, Alain
    • Analytical and Bioanalytical Chemistry, Vol. 410, Issue 19
    • DOI: 10.1007/s00216-018-0878-0

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


    Faster dispersive liquid-liquid microextraction methods using magnetic ionic liquids as solvents
    journal, September 2016


    Thermophysical and magnetic studies of two paramagnetic liquid salts: [C4mim][FeCl4] and [P66614][FeCl4]
    journal, July 2013


    Solubility and phase behavior of binary systems containing salts based on transitional metals
    journal, August 2013

    • Zakrzewska, Małgorzata E.; Paninho, Ana B.; Môlho, Marta F.
    • The Journal of Chemical Thermodynamics, Vol. 63
    • DOI: 10.1016/j.jct.2013.03.014

    Highly efficient extraction of phenolic compounds by use of magnetic room temperature ionic liquids for environmental remediation
    journal, September 2011


    Tetraalkylphosphonium-based ionic liquids
    journal, May 2005

    • Del Sesto, Rico E.; Corley, Cynthia; Robertson, Al
    • Journal of Organometallic Chemistry, Vol. 690, Issue 10, p. 2536-2542
    • DOI: 10.1016/j.jorganchem.2004.09.060

    Preparation and evaluation of cellulose-dissolving magnetic ionic liquid
    journal, June 2013


    Friedel-Crafts acylation of aromatics catalysed by supported ionic liquids
    journal, July 2001


    Paramagnetic Ionic Liquids for Measurements of Density Using Magnetic Levitation
    journal, August 2013

    • Bwambok, David K.; Thuo, Martin M.; Atkinson, Manza B. J.
    • Analytical Chemistry, Vol. 85, Issue 17
    • DOI: 10.1021/ac401899u

    Trigonal Tricationic Ionic Liquids: A Generation of Gas Chromatographic Stationary Phases
    journal, January 2009

    • Payagala, Tharanga; Zhang, Ying; Wanigasekara, Eranda
    • Analytical Chemistry, Vol. 81, Issue 1
    • DOI: 10.1021/ac8016949

    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

    Solvatochromic Dyes as Solvent Polarity Indicators
    journal, December 1994


    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

    A demonstration of crystal-field effects in octahedral complexes
    journal, October 1996

    • Koubek, Edward; Elert, Mark
    • Journal of Chemical Education, Vol. 73, Issue 10
    • DOI: 10.1021/ed073p947

    Using a Combination of Experimental and Computational Methods To Explore the Impact of Metal Identity and Ligand Field Strength on the Electronic Structure of Metal Ions
    journal, September 2011

    • Pernicone, Naomi C.; Geri, Jacob B.; York, John T.
    • Journal of Chemical Education, Vol. 88, Issue 9
    • DOI: 10.1021/ed1010079

    Extractive Desulfurization Using Fe-Containing Ionic Liquids
    journal, May 2008

    • Ko, Nan Hee; Lee, Je Seung; Huh, Eun Soo
    • Energy & Fuels, Vol. 22, Issue 3
    • DOI: 10.1021/ef7007369

    Application of Iron-Containing Magnetic Ionic Liquids in Extraction Process of Coal Direct Liquefaction Residues
    journal, February 2012

    • Wang, Jieli; Yao, Hongwei; Nie, Yi
    • Industrial & Engineering Chemistry Research, Vol. 51, Issue 9
    • DOI: 10.1021/ie202940k

    Metal isotope effect on metal-ligand vibrations. IV. Metal complexes of acetylacetone
    journal, July 1970

    • Nakamoto, Kazuo.; Udovich, Carl.; Takemoto, James.
    • Journal of the American Chemical Society, Vol. 92, Issue 13
    • DOI: 10.1021/ja00716a024

    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

    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

    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

    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

    Electrochromic and magnetic ionic liquids
    journal, January 2011

    • Branco, Aida; Branco, Luís C.; Pina, Fernando
    • Chem. Commun., Vol. 47, Issue 8
    • DOI: 10.1039/c0cc03892j

    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

    Sonochemical formation of iron oxide nanoparticles in ionic liquids for magnetic liquid marble
    journal, January 2012

    • Zhang, Shiguo; Zhang, Yan; Wang, Ying
    • Physical Chemistry Chemical Physics, Vol. 14, Issue 15
    • DOI: 10.1039/c2cp23675c

    Dication magnetic ionic liquids with tuneable heteroanions
    journal, January 2013

    • Brown, Paul; Butts, Craig P.; Eastoe, Julian
    • Chemical Communications, Vol. 49, Issue 27
    • DOI: 10.1039/c3cc00103b

    Synthesis and characterization of low viscosity hexafluoroacetylacetonate-based hydrophobic magnetic ionic liquids
    journal, January 2017

    • Pierson, Stephen A.; Nacham, Omprakash; Clark, Kevin D.
    • New Journal of Chemistry, Vol. 41, Issue 13
    • DOI: 10.1039/c7nj00206h

    Magnetic ionic liquids based on transition metal complexes with N -alkylimidazole ligands
    journal, January 2019

    • Chand, Deepak; Farooq, Muhammad Qamar; Pathak, Arjun K.
    • New Journal of Chemistry, Vol. 43, Issue 1
    • DOI: 10.1039/c8nj05176c

    A new class of magnetic fluids: bmim[FeCl/sub 4/] and nbmim[FeCl/sub 4/] ionic liquids
    journal, January 2006


    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

    Metallocenium Ionic Liquids
    journal, June 2010

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