Post-synthetic modification of ionic liquids using ligand-exchange and redox coordination chemistry

2020 ◽  
Vol 8 (43) ◽  
pp. 22674-22685
Author(s):  
Michael A. LeRoy ◽  
Austin M. Mroz ◽  
Jenna L. Mancuso ◽  
Aaron Miller ◽  
Allison Van Cleve ◽  
...  
Keyword(s):  
Ionic Liquids ◽  
Coordination Chemistry ◽  
Ligand Exchange

Ionic liquids (ILs) derive their useful properties from molecularly tunable compositions, but methods to diversify anion identities and probe ion speciation remain limited.

Post-Synthetic Modification of Ionic Liquids Using Ligand-Exchange and Redox Coordination Chemistry

2020 ◽  
Author(s):  
Michael LeRoy ◽  
Austin Mroz ◽  
Jenna L. Mancuso ◽  
Aaron Miller ◽  
Allison Van Cleve ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Coordination Chemistry ◽  
Ligand Exchange ◽  
Covalent Bonding ◽  
Anion Coordination ◽  
Rheological Measurements ◽  
Vis Spectroscopy ◽  
Wide Range ◽  
Coordination Spheres

Ionic liquids (ILs) derive their useful properties from molecularly tunable compositions, but methods to diversify anion identities and probe ion speciation remain limited. Here, we demonstrate post-synthetic modification of perhalometallate anions to achieve ionic liquid-to-ionic liquid transformations. Rheological measurements of the metal-containing ILs indicate that minor alterations to anion coordination spheres induces considerable changes to IL viscosities. UV-vis spectra confirm the purities for most ILs, while revealing a surprising cation dependence of perchlorovanadate speciation and supramolecular structure. The intermolecular interactions studied here span a wide range from dispersion to covalent bonding, permitting their impact on IL viscosity to be decoupled and quantified. Together, synthetic strategies from coordination chemistry paired with conventional UV-vis spectroscopy provide a powerful tool for expanding IL compositions and investigating fundamental nanoscale behavior.

Post-Synthetic Modification of Ionic Liquids Using Ligand-Exchange and Redox Coordination Chemistry

2020 ◽  
Author(s):  
Michael LeRoy ◽  
Austin Mroz ◽  
Jenna L. Mancuso ◽  
Aaron Miller ◽  
Allison Van Cleve ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Coordination Chemistry ◽  
Ligand Exchange ◽  
Covalent Bonding ◽  
Anion Coordination ◽  
Rheological Measurements ◽  
Vis Spectroscopy ◽  
Wide Range ◽  
Coordination Spheres

Ionic liquids (ILs) derive their useful properties from molecularly tunable compositions, but methods to diversify anion identities and probe ion speciation remain limited. Here, we demonstrate post-synthetic modification of perhalometallate anions to achieve ionic liquid-to-ionic liquid transformations. Rheological measurements of the metal-containing ILs indicate that minor alterations to anion coordination spheres induces considerable changes to IL viscosities. UV-vis spectra confirm the purities for most ILs, while revealing a surprising cation dependence of perchlorovanadate speciation and supramolecular structure. The intermolecular interactions studied here span a wide range from dispersion to covalent bonding, permitting their impact on IL viscosity to be decoupled and quantified. Together, synthetic strategies from coordination chemistry paired with conventional UV-vis spectroscopy provide a powerful tool for expanding IL compositions and investigating fundamental nanoscale behavior.

Coordination chemistry of the bis(trifluoromethylsulfonyl)imide anion: molecular interactions in room temperature ionic liquids

2005 ◽  
pp. 1438 ◽  
Author(s):  
D. Bridget WilliamsCurrently at the Department ◽  
Michael E. Stoll ◽  
Brian L. Scott ◽  
David A. Costa ◽  
Warren J. Oldham, Jr.
Keyword(s):  
Ionic Liquids ◽  
Coordination Chemistry ◽  
Molecular Interactions ◽  
Room Temperature ◽  
Room Temperature Ionic Liquids

scholarly journals A Free Aluminylene with Diverse σ-Donating and Doubly σ/π-Accepting Ligand Features for Transition Metals

2021 ◽  
Author(s):  
Xin Zhang ◽  
Liu Leo Liu
Keyword(s):  
Density Functional Theory ◽  
Coordination Chemistry ◽  
Transition Metals ◽  
Electronic Structures ◽  
Ligand Exchange ◽  
Density Functional ◽  
Reduction Reaction ◽  
Functional Theory ◽  
Metal Centers ◽  
Coordination Behavior

We report herein the synthesis, characterization, and coordination chemistry of a free N-aluminylene, namely a carbazolylaluminylene 2b. This species is prepared via a reduction reaction of the corresponding carbazolyl aluminium diiodide. The coordination behavior of 2b towards transition metal centers (W, Cr) is shown to afford a series of novel aluminylene complexes 3-6 with diverse coordination modes. We demonstrate that the Al center in 2b can behave as: 1. a σ-donating and doubly π-accepting ligand; 2. a σ-donating, σ-accepting and π-accepting ligand; and 3. a σ-donating and doubly σ-accepting ligand. Additionally, we show ligand exchange at the aluminylene center providing access to the modulation of electronic properties of transition metals without changing the coordinated atoms. Investigations of 2b with IDippCuCl (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) show an unprecedented aluminylene-alumanyl transformation leading to a rare terminal Cu-alumanyl complex 8. The electronic structures of such complexes and the mechanism of the aluminylene-alumanyl transformation are investigated through density functional theory (DFT) calculations.

Isoleucine ionic liquids as additives to separate mandelic acid and their derivative enantiomers by HPLC

2014 ◽  
Vol 6 (15) ◽  
pp. 5627-5631 ◽  
Author(s):  
Jie Zhou ◽  
Suzhen Zhao ◽  
Guangjun Fu ◽  
Zhenzhong Zhang
Keyword(s):  
Ionic Liquids ◽  
Ligand Exchange ◽  
Mandelic Acid ◽  
Exchange Chromatography ◽  
Chiral Ligands ◽  
Chiral Ligand ◽  
Ligand Exchange Chromatography ◽  
Chiral Ligand Exchange

In this study, functional isoleucine ionic liquids were synthesized and used as novel chiral ligands coordinated with Cu(ii) in chiral ligand exchange chromatography.

Spin-labelled Ligands

1974 ◽  
Vol 52 (13) ◽  
pp. 2454-2462 ◽  
Author(s):  
C. T. Cazianis ◽  
D. R. Eaton
Keyword(s):  
Coordination Chemistry ◽  
Unpaired Electron ◽  
Ligand Exchange ◽  
Metal Ion ◽  
Functional Group ◽  
Lewis Base ◽  
Exchange Reactions ◽  
Base Site ◽  
Relative Electron ◽  
A Site

A spin-labelled ligand is defined as a molecule with two functional groups, one of which provides a Lewis base site suitable for complexing to a metal ion. The second functional group comprises a site bearing an unpaired electron. The possible utility of such compounds in coordination chemistry has been explored. The spin density distribution in 4-pyridyl-t-butyl nitroxide provides information on the relative electron accepting abilities of different metal ions in various ligand environments. A method for measuring the rates of very rapid ligand exchange reactions is also suggested.

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