Dicationic ionic liquid crystals: Synthesis, characterization, optical properties, and ionic conductivity of bis(4-oligoethyleneoxyphenyl) viologen bistosylate salts

Pradip K. Bhowmik; Si L. Chen; David King; Haesook Han; Zane Bolyard; Christopher Schmiedl; Michael R. Fisch; Sanjeev R. Gopal; Thamil Selvi Velayutham; Alfonso Martinez-Felipe

doi:10.1016/j.molliq.2024.124140

Dicationic ionic liquid crystals: Synthesis, characterization, optical properties, and ionic conductivity of bis(4-oligoethyleneoxyphenyl) viologen bistosylate salts

Pradip K. Bhowmik^* (Corresponding Author), Si L. Chen, David King, Haesook Han, Zane Bolyard, Christopher Schmiedl, Michael R. Fisch, Sanjeev R. Gopal, Thamil Selvi Velayutham, Alfonso Martinez-Felipe

^*Corresponding author for this work

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Abstract

Three bis(4-oligoethyleneoxyphenyl) viologen bistosylate salts of different lengths were prepared via the Zincke reaction followed by a metathesis reaction with silver tosylate, and their chemical structures confirmed by ¹H, ¹³C nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) techniques, and elemental analysis. Thermogravimetric analysis (TGA) showed these salts had excellent thermal stabilities, losing just 5 % of their initial mass between 283 and 288 °C. Liquid crystalline phases and transition temperatures were determined by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and variable temperature X-ray diffraction (VTXRD) techniques. The salts exhibited weak fluorescent emission in dichloromethane and no emission in acetonitrile but exhibited light emission in the solid state. Their absolute quantum yields ranged between 3 and 12 %. Impedance spectroscopy showed that the ionic conductivity of the salts increases with the number of oxyethylene units in the extended viologen moiety. The salt-containing four oxyethylene units at each end reach a conductivity value of 10^-2 S·cm⁻¹, attributed to its larger molecular flexibility and improved ionic liquid mobility.

Original language	English
Article number	124140
Number of pages	11
Journal	Journal of molecular liquids
Volume	398
Early online date	7 Feb 2024
DOIs	https://doi.org/10.1016/j.molliq.2024.124140
Publication status	Published - 15 Mar 2024

Bibliographical note

Funding Information:
PKB sincerely acknowledges the Knowledge Fund that is administered by the Nevada Governor’s Office of Economic Development (GOED) and the University of Nevada Las Vegas (UNLV). HH sincerely acknowledges the Faculty Opportunity Award (FOA) that is administered by the Office of Sponsored Programs (OSP) at UNLV. MRF sincerely acknowledges the Petroleum Research Fund (Grant 59345-ND7) and National Science Foundation USA (Grant NSF-DMR-2211347) for their support of this research. TSV acknowledges the Ministry of Higher Education of Malaysia through the Fundamental Research Grant Scheme [FRGS/1/2018/STG07/UM/02/6]. AMF would like to thank the Carnegie Trust for the Universities of Scotland, for the Research Incentive Grant RIG008586, the Royal Society and Specac Ltd., for the Research Grant RGS\R1\201397, and the Royal Society of Chemistry for the award of a mobility grant (M19-0000).

Keywords

Dielectric spectroscopy
Differential scanning calorimetry
Ionic conductivity
Ionic liquid crystals
Polarized optical microscopy
Variable temperature X-ray diffraction

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Bhowmik, P. K., Chen, S. L., King, D., Han, H., Bolyard, Z., Schmiedl, C., Fisch, M. R., Gopal, S. R., Selvi Velayutham, T., & Martinez-Felipe, A. (2024). Dicationic ionic liquid crystals: Synthesis, characterization, optical properties, and ionic conductivity of bis(4-oligoethyleneoxyphenyl) viologen bistosylate salts. Journal of molecular liquids, 398, Article 124140. https://doi.org/10.1016/j.molliq.2024.124140

Dicationic ionic liquid crystals: Synthesis, characterization, optical properties, and ionic conductivity of bis(4-oligoethyleneoxyphenyl) viologen bistosylate salts. / Bhowmik, Pradip K. (Corresponding Author); Chen, Si L.; King, David et al.
In: Journal of molecular liquids, Vol. 398, 124140, 15.03.2024.

Research output: Contribution to journal › Article › peer-review

Bhowmik, PK, Chen, SL, King, D, Han, H, Bolyard, Z, Schmiedl, C, Fisch, MR, Gopal, SR, Selvi Velayutham, T & Martinez-Felipe, A 2024, 'Dicationic ionic liquid crystals: Synthesis, characterization, optical properties, and ionic conductivity of bis(4-oligoethyleneoxyphenyl) viologen bistosylate salts', Journal of molecular liquids, vol. 398, 124140. https://doi.org/10.1016/j.molliq.2024.124140

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title = "Dicationic ionic liquid crystals: Synthesis, characterization, optical properties, and ionic conductivity of bis(4-oligoethyleneoxyphenyl) viologen bistosylate salts",

abstract = "Three bis(4-oligoethyleneoxyphenyl) viologen bistosylate salts of different lengths were prepared via the Zincke reaction followed by a metathesis reaction with silver tosylate, and their chemical structures confirmed by 1H, 13C nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) techniques, and elemental analysis. Thermogravimetric analysis (TGA) showed these salts had excellent thermal stabilities, losing just 5 % of their initial mass between 283 and 288 °C. Liquid crystalline phases and transition temperatures were determined by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and variable temperature X-ray diffraction (VTXRD) techniques. The salts exhibited weak fluorescent emission in dichloromethane and no emission in acetonitrile but exhibited light emission in the solid state. Their absolute quantum yields ranged between 3 and 12 %. Impedance spectroscopy showed that the ionic conductivity of the salts increases with the number of oxyethylene units in the extended viologen moiety. The salt-containing four oxyethylene units at each end reach a conductivity value of 10-2 S·cm−1, attributed to its larger molecular flexibility and improved ionic liquid mobility.",

keywords = "Dielectric spectroscopy, Differential scanning calorimetry, Ionic conductivity, Ionic liquid crystals, Polarized optical microscopy, Variable temperature X-ray diffraction",

author = "Bhowmik, {Pradip K.} and Chen, {Si L.} and David King and Haesook Han and Zane Bolyard and Christopher Schmiedl and Fisch, {Michael R.} and Gopal, {Sanjeev R.} and {Selvi Velayutham}, Thamil and Alfonso Martinez-Felipe",

note = "Funding Information: PKB sincerely acknowledges the Knowledge Fund that is administered by the Nevada Governor{\textquoteright}s Office of Economic Development (GOED) and the University of Nevada Las Vegas (UNLV). HH sincerely acknowledges the Faculty Opportunity Award (FOA) that is administered by the Office of Sponsored Programs (OSP) at UNLV. MRF sincerely acknowledges the Petroleum Research Fund (Grant 59345-ND7) and National Science Foundation USA (Grant NSF-DMR-2211347) for their support of this research. TSV acknowledges the Ministry of Higher Education of Malaysia through the Fundamental Research Grant Scheme [FRGS/1/2018/STG07/UM/02/6]. AMF would like to thank the Carnegie Trust for the Universities of Scotland, for the Research Incentive Grant RIG008586, the Royal Society and Specac Ltd., for the Research Grant RGS\R1\201397, and the Royal Society of Chemistry for the award of a mobility grant (M19-0000). ",

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doi = "10.1016/j.molliq.2024.124140",

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AU - Bhowmik, Pradip K.

AU - Chen, Si L.

AU - King, David

AU - Han, Haesook

AU - Bolyard, Zane

AU - Schmiedl, Christopher

AU - Fisch, Michael R.

AU - Gopal, Sanjeev R.

AU - Selvi Velayutham, Thamil

AU - Martinez-Felipe, Alfonso

N1 - Funding Information: PKB sincerely acknowledges the Knowledge Fund that is administered by the Nevada Governor’s Office of Economic Development (GOED) and the University of Nevada Las Vegas (UNLV). HH sincerely acknowledges the Faculty Opportunity Award (FOA) that is administered by the Office of Sponsored Programs (OSP) at UNLV. MRF sincerely acknowledges the Petroleum Research Fund (Grant 59345-ND7) and National Science Foundation USA (Grant NSF-DMR-2211347) for their support of this research. TSV acknowledges the Ministry of Higher Education of Malaysia through the Fundamental Research Grant Scheme [FRGS/1/2018/STG07/UM/02/6]. AMF would like to thank the Carnegie Trust for the Universities of Scotland, for the Research Incentive Grant RIG008586, the Royal Society and Specac Ltd., for the Research Grant RGS\R1\201397, and the Royal Society of Chemistry for the award of a mobility grant (M19-0000).

PY - 2024/3/15

Y1 - 2024/3/15

N2 - Three bis(4-oligoethyleneoxyphenyl) viologen bistosylate salts of different lengths were prepared via the Zincke reaction followed by a metathesis reaction with silver tosylate, and their chemical structures confirmed by 1H, 13C nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) techniques, and elemental analysis. Thermogravimetric analysis (TGA) showed these salts had excellent thermal stabilities, losing just 5 % of their initial mass between 283 and 288 °C. Liquid crystalline phases and transition temperatures were determined by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and variable temperature X-ray diffraction (VTXRD) techniques. The salts exhibited weak fluorescent emission in dichloromethane and no emission in acetonitrile but exhibited light emission in the solid state. Their absolute quantum yields ranged between 3 and 12 %. Impedance spectroscopy showed that the ionic conductivity of the salts increases with the number of oxyethylene units in the extended viologen moiety. The salt-containing four oxyethylene units at each end reach a conductivity value of 10-2 S·cm−1, attributed to its larger molecular flexibility and improved ionic liquid mobility.

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KW - Ionic conductivity

KW - Ionic liquid crystals

KW - Polarized optical microscopy

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Dicationic ionic liquid crystals: Synthesis, characterization, optical properties, and ionic conductivity of bis(4-oligoethyleneoxyphenyl) viologen bistosylate salts

Abstract

Bibliographical note

Keywords

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