Choline Fluoride-Ethylene glycol deep eutectic solvent mixture – Synthesis and physicochemical properties

Alfurayj, Ibrahim; Pandian, Rathiesh; Springer, Sarah; Burda, Clemens

doi:10.1016/j.molliq.2023.122454

Choline Fluoride-Ethylene glycol deep eutectic solvent mixture – Synthesis and physicochemical properties

Journal Article · Tue Jun 27 00:00:00 UTC 2023 · Journal of Molecular Liquids

DOI:https://doi.org/10.1016/j.molliq.2023.122454· OSTI ID:2421277

^[1]; ^[2]; Springer, Sarah ^[2]; ^[2]

Case Western Reserve Univ., Cleveland, OH (United States); OSTI
Case Western Reserve Univ., Cleveland, OH (United States)

A critical factor in achieving tunability in DESs is varying the type of hydrogen bond acceptors (HBAs) and donors (HBDs). Choline halides (ChX), such as ChCl and ChBr, have been studied to investigate the effect of the choline anion on DESs. However, ChF-based DESs have been underrepresented in scientific research. ChF has excellent potential, such as high electron affinity, ionization potential, and strong hydrogen bond interactions. Moreover, ChF-based DES can lead to a deeper understanding of DESs due to the NMR-active 19F nuclear spin nature. We report the first synthesis and characterization of choline fluoride-EG (1:2, ChF:EG) DES, which we named “EthalineF.” We studied this mixture using various spectroscopic techniques, including NMR, FT-IR, Raman, and UV–vis spectroscopies. Polarity, density, viscosity, and conductivity measurements were collected as well. Transient absorption spectroscopy (TAS) was used to study the solvation dynamics of EthalineF. 19F NMR indicated that some fluoride anions (~15%) are coordinated to the choline cation. In EthalineF, the new type of observed fluoride anions is proposed to be a tight-binding choline-fluoride ion pair. Further, EthalineF has a larger solvodynamic radius than Ethaline. This can explain the lower conductivity for EthalineF compared to Ethaline despite the higher fluidity and solvation dynamics for EthalineF.

View Accepted Manuscript (DOE)

Research Organization:: Case Western Reserve Univ., Cleveland, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019409

OSTI ID:: 2421277

Journal Information:: Journal of Molecular Liquids, Journal Name: Journal of Molecular Liquids Journal Issue: C Vol. 386; ISSN 0167-7322

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

Solvents and Solvent Effects in Organic Chemistry Reichardt, Christian; Welton, Thomas https://doi.org/10.1002/9783527632220	book	October 2010
Über Pyridinium-N-phenol-betaine und ihre Verwendung zur Charakterisierung der Polarität von Lösungsmitteln Dimroth, Karl; Reichardt, Christian; Siepmann, Theodor Justus Liebigs Annalen der Chemie, Vol. 661, Issue 1 https://doi.org/10.1002/jlac.19636610102	journal	February 1963
A Raman spectroscopic study of aqueous and methanolic tetramethylammonium chloride solutions Kabisch†, G.; Klose, M. Journal of Raman Spectroscopy, Vol. 7, Issue 6 https://doi.org/10.1002/jrs.1250070604	journal	December 1978
Solvent polarity scales: determination of new E _T (30) values for 84 organic solvents: SOLVENT POLARITY SCALES Cerón-Carrasco, José P.; Jacquemin, Denis; Laurence, Christian Journal of Physical Organic Chemistry, Vol. 27, Issue 6 https://doi.org/10.1002/poc.3293	journal	February 2014
Raman and infrared spectra of ethylene glycol Krishnan, K.; Krishnan, R. S. Proceedings of the Indian Academy of Sciences - Section A, Vol. 64, Issue 2 https://doi.org/10.1007/BF03047675	journal	August 1966
Specific excitation of the solvent coordinate in the S3→S1 and S1→S0 radiationless decay of the betaines Levinger, Nancy E.; Johnson, Alan E.; Walker, Gilbert C. Chemical Physics Letters, Vol. 196, Issue 1-2 https://doi.org/10.1016/0009-2614(92)85947-9	journal	August 1992
Hydrogen bonding Harmon, Kenneth M.; Avci, Günsel F. Journal of Molecular Structure, Vol. 118, Issue 3-4 https://doi.org/10.1016/0022-2860(84)87223-3	journal	September 1984
Hydrogen bonding Harmon, Kenneth M.; Madeira, Susan L.; Jacks, Marshan J. Journal of Molecular Structure, Vol. 128, Issue 4 https://doi.org/10.1016/0022-2860(85)85006-7	journal	May 1985
Hydrogen bonding Harmon, Kenneth M.; Avci, Günsel F.; Desantis, Nancy J. Journal of Molecular Structure, Vol. 128, Issue 4 https://doi.org/10.1016/0022-2860(85)85007-9	journal	May 1985
Hydrogen bonding Harmon, Kenneth M.; Akin, Anne C.; Avci, Günsel F. Journal of Molecular Structure, Vol. 244 https://doi.org/10.1016/0022-2860(91)80158-Z	journal	April 1991
Ultrafast electron transfer of betaine-30 Scholz, R.; Darwish, M.; Schreiber, M. Journal of Luminescence, Vol. 76-77 https://doi.org/10.1016/S0022-2313(97)00226-3	journal	February 1998
Ionic deep eutectic solvents for the extraction and separation of natural products Huang, Jie; Guo, Xiuyun; Xu, Tianyi Journal of Chromatography A, Vol. 1598 https://doi.org/10.1016/j.chroma.2019.03.046	journal	August 2019
Deep eutectic solvents: A structural point of view on the role of the anion Migliorati, Valentina; D’Angelo, Paola Chemical Physics Letters, Vol. 777 https://doi.org/10.1016/j.cplett.2021.138702	journal	August 2021
A novel deep eutectic solvent-based ionic liquid used as electrolyte for dye-sensitized solar cells Jhong, Huei-Ru; Wong, David Shan-Hill; Wan, Chi-Chao Electrochemistry Communications, Vol. 11, Issue 1 https://doi.org/10.1016/j.elecom.2008.11.001	journal	January 2009
Self-assembled core–shell clusters in deep eutectic solvents based on tetra-n-alkylammonium cations for high dissolution of strongly hydrogen-bonded small molecules Jia, Jianhui; Chen, Jian-Bo; Du, Jianglong Journal of Colloid and Interface Science, Vol. 628 https://doi.org/10.1016/j.jcis.2022.07.140	journal	December 2022
Pressure-induced amorphization and crystallization of Choline chloride/Ethylene glycol deep eutectic solvent Chu, Kunkun; Yuan, Chaosheng; Li, Haining Journal of Molecular Liquids, Vol. 242 https://doi.org/10.1016/j.molliq.2017.06.129	journal	September 2017
NMR study of choline chloride-based deep eutectic solvents Delso, Ignacio; Lafuente, Carlos; Muñoz-Embid, José Journal of Molecular Liquids, Vol. 290 https://doi.org/10.1016/j.molliq.2019.111236	journal	September 2019
Mixtures of tetrabutylammonium chloride salt with different glycol structures: Thermal stability and functional groups characterizations Majid, Mohd Faridzuan; Mohd Zaid, Hayyiratul Fatimah; Kait, Chong Fai Journal of Molecular Liquids, Vol. 294 https://doi.org/10.1016/j.molliq.2019.111588	journal	November 2019
New deep eutectic solvents based on ethylene glycol - LiTFSI and their application as an electrolyte in electrochemical double layer capacitor (EDLC) Tran, Kieu T. T.; Le, Linh T. M.; Phan, An L. B. Journal of Molecular Liquids, Vol. 320 https://doi.org/10.1016/j.molliq.2020.114495	journal	December 2020
Synthesis and characterization of a computationally predicted redox and radiation stable deep eutectic solvent Das, Laboni; Mukherjee, Sumanta; Kumar Maity, Dilip Journal of Molecular Liquids, Vol. 360 https://doi.org/10.1016/j.molliq.2022.119377	journal	August 2022
Bio-inspired choline chloride-based deep eutectic solvents as electrolytes for lithium-ion batteries Millia, Luca; Dall'Asta, Valentina; Ferrara, Chiara Solid State Ionics, Vol. 323 https://doi.org/10.1016/j.ssi.2018.05.016	journal	October 2018
Deep Eutectic Solvents: A Review of Fundamentals and Applications Hansen, Benworth B.; Spittle, Stephanie; Chen, Brian Chemical Reviews, Vol. 121, Issue 3 https://doi.org/10.1021/acs.chemrev.0c00385	journal	December 2020
Ethylene Glycol Dihedral Angle Dynamics: Relating Molecular Conformation to the Raman Spectrum of the Liquid Jindal, Aman; Vasudevan, Sukumaran The Journal of Physical Chemistry B, Vol. 125, Issue 7 https://doi.org/10.1021/acs.jpcb.0c10921	journal	February 2021
Solvation Dynamics of Wet Ethaline: Water is the Magic Component Alfurayj, Ibrahim; Fraenza, Carla Cecilia; Zhang, Yong The Journal of Physical Chemistry B, Vol. 125, Issue 31 https://doi.org/10.1021/acs.jpcb.1c04629	journal	August 2021
Quantum Chemical Insight into the Interactions and Thermodynamics Present in Choline Chloride Based Deep Eutectic Solvents Wagle, Durgesh V.; Deakyne, Carol A.; Baker, Gary A. The Journal of Physical Chemistry B, Vol. 120, Issue 27 https://doi.org/10.1021/acs.jpcb.6b04750	journal	June 2016
Redox-Active Eutectic Electrolyte with Viologen and Ferrocene Derivatives for Flow Batteries Ghahremani, Raziyeh; Dean, William; Sinclair, Nicholas ACS Applied Materials & Interfaces, Vol. 15, Issue 1 https://doi.org/10.1021/acsami.2c18546	journal	December 2022
Deep Eutectic Solvents as Suitable Electrolytes for Electrochromic Devices Cruz, Hugo; Jordão, Noémi; Amorim, Patrícia ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 2 https://doi.org/10.1021/acssuschemeng.7b03684	journal	December 2017
Direct determination by Raman scattering of the conformation of the choline group in phospholipid bilayers Akutsu, Hideo Biochemistry, Vol. 20, Issue 26 https://doi.org/10.1021/bi00529a006	journal	December 1981
Solvatochromic Dyes as Solvent Polarity Indicators Reichardt, Christian Chemical Reviews, Vol. 94, Issue 8 https://doi.org/10.1021/cr00032a005	journal	December 1994
Deep Eutectic Solvents (DESs) and Their Applications Smith, Emma L.; Abbott, Andrew P.; Ryder, Karl S. Chemical Reviews, Vol. 114, Issue 21 https://doi.org/10.1021/cr300162p	journal	October 2014
Pyridinium N-Phenolate Betaine Dyes Machado, Vanderlei G.; Stock, Rafaela I.; Reichardt, Christian Chemical Reviews, Vol. 114, Issue 20 https://doi.org/10.1021/cr5001157	journal	September 2014
Dynamic Solvent Effect on Betaine-30 Electron-Transfer Kinetics in Alcohols Reid, Philip J.; Barbara, Paul F. The Journal of Physical Chemistry, Vol. 99, Issue 11 https://doi.org/10.1021/j100011a024	journal	March 1995
Long-Range Electrostatic Colloidal Interactions and Specific Ion Effects in Deep Eutectic Solvents Sanchez-Fernandez, Adrian; Jackson, Andrew J.; Prévost, Sylvain F. Journal of the American Chemical Society, Vol. 143, Issue 35 https://doi.org/10.1021/jacs.1c04781	journal	August 2021
Hydrogen Bonds and Conformations in Ethylene Glycol under Pressure Murli, Chitra; Lu, Ning; Dong, Zhaohui The Journal of Physical Chemistry B, Vol. 116, Issue 41 https://doi.org/10.1021/jp306220q	journal	October 2012
Determination of a Solvent Hydrogen-Bond Acidity Scale by Means of the Solvatochromism of Pyridinium- N -phenolate Betaine Dye 30 and PCM-TD-DFT Calculations Cerón-Carrasco, José P.; Jacquemin, Denis; Laurence, Christian The Journal of Physical Chemistry B, Vol. 118, Issue 17 https://doi.org/10.1021/jp501534n	journal	April 2014
Computer Simulations of the Solvatochromism of Betaine-30 Mente, S. R.; Maroncelli, M. The Journal of Physical Chemistry B, Vol. 103, Issue 36 https://doi.org/10.1021/jp991549r	journal	September 1999
Natural Deep Eutectic Solvents – Solvents for the 21st Century Paiva, Alexandre; Craveiro, Rita; Aroso, Ivo ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 5 https://doi.org/10.1021/sc500096j	journal	March 2014
How polar are choline chloride-based deep eutectic solvents? Pandey, Ashish; Rai, Rewa; Pal, Mahi Phys. Chem. Chem. Phys., Vol. 16, Issue 4 https://doi.org/10.1039/C3CP53456A	journal	January 2014
Deep eutectic solvents (DESs) as low-cost and green electrolytes for electrochromic devices Cruz, Hugo; Jordão, Noémi; Branco, Luís C. Green Chemistry, Vol. 19, Issue 7 https://doi.org/10.1039/C7GC00347A	journal	January 2017
Novel solvent properties of choline chloride/urea mixturesElectronic supplementary information (ESI) available: spectroscopic data. See http://www.rsc.org/suppdata/cc/b2/b210714g/ Abbott, Andrew P.; Capper, Glen; Davies, David L. Chemical Communications, Issue 1 https://doi.org/10.1039/b210714g	journal	November 2002
Polarity of ionic liquids determined empirically by means of solvatochromic pyridinium N-phenolate betaine dyes Reichardt, Christian Green Chemistry, Vol. 7, Issue 5 https://doi.org/10.1039/b500106b	journal	January 2005
Deep eutectic solvents: syntheses, properties and applications Zhang, Qinghua; De Oliveira Vigier, Karine; Royer, Sébastien Chemical Society Reviews, Vol. 41, Issue 21 https://doi.org/10.1039/c2cs35178a	journal	January 2012
Deep eutectic solvents—The vital link between ionic liquids and ionic solutions Abbott, Andrew P.; Edler, Karen J.; Page, Alister J. The Journal of Chemical Physics, Vol. 155, Issue 15 https://doi.org/10.1063/5.0072268	journal	October 2021
Structure of liquid ethylene glycol Rodnikova, M. N.; Chumaevskii, N. A.; Troitskii, V. M. Russian Journal of Physical Chemistry, Vol. 80, Issue 5 https://doi.org/10.1134/S0036024406050293	journal	May 2006
Perspective—Semi-Solid Electrolytes Based on Deep Eutectic Solvents: Opportunities and Future Directions Navarro-Suárez, A. M.; Johansson, P. Journal of The Electrochemical Society, Vol. 167, Issue 7 https://doi.org/10.1149/1945-7111/ab68d3	journal	January 2020
Fluoride Ionic Liquids in Salts of Ethylmethylimidazolium and Substituted Cyclopropenium Cation Families Curnow, Owen J.; MacFarlane, Douglas R.; Walst, Kelvin J. Frontiers in Chemistry, Vol. 6 https://doi.org/10.3389/fchem.2018.00603	journal	December 2018
Hygroscopicity of 1:2 Choline Chloride:Ethylene Glycol Deep Eutectic Solvent: A Hindrance to its Electroplating Industry Adoption Brusas, John Raymund; Dela Pena, Eden May B. Journal of Electrochemical Science and Technology, Vol. 12, Issue 4 https://doi.org/10.33961/jecst.2020.01522	journal	November 2021
Novel Contribution to the Chemical Structure of Choline Chloride Based Deep Eutectic Solvents Aissaoui, Tayeb Pharmaceutica Analytica Acta, Vol. 6, Issue 11 https://doi.org/10.4172/2153-2435.1000448	journal	January 2015

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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fs-TAS

Choline Fluoride-Ethylene glycol deep eutectic solvent mixture – Synthesis and physicochemical properties

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