Pulse Radiolysis and Computational Studies on a Pyrrolidinium Dicyanamide Ionic Liquid: Detection of the Dimer Radical Anion

Das, Laboni; Kumar, Rahul; Maity, Dilip K.; Adhikari, Soumyakanti; Dhiman, Surajdevprakash B.; Wishart, James F.

doi:10.1021/acs.jpca.8b00978

Title: Pulse Radiolysis and Computational Studies on a Pyrrolidinium Dicyanamide Ionic Liquid: Detection of the Dimer Radical Anion

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Abstract

A pulse radiolysis study on pyrrolidinium cation based ionic liquids is presented here in this paper. Time-resolved absorption spectra for 1-methyl-1-propylpyrrolidinium dicyanamide (DCA) at 500 ns after the electron pulse show broad absorption bands at wavelengths below 440 nm and at 640 nm. In pyrrolidinium bis(trifluoromethylsulfonyl)imide (NTf₂) and tris(perfluoroethyl)trifluorophosphate (FAP) ILs, the transient absorption below 440 nm is much weaker. The absorption at 500 ns, which increases with wavelength from 500 nm to beyond 800 nm, was assigned to the tail of the solvated electron NIR absorption spectrum, since it disappears in the presence of N₂O. In the DCA IL, the presence of a reducing species was confirmed by the formation of pyrene radical anion. The difference in the transient species in the case of the DCA IL compared to other two ILs should be due to the anion, with cations being similar. In pseudohalide ILs such as DCA, radicals are formed by direct hole trapping by the anion (X^– + h⁺ → X•), followed by addition to the parent anion. Prediction of the UV/vis absorption spectra of the dimer radical anion by computational calculation supports the experimental results. The oxidizing efficiency of (DCA)₂•– and its reduction potential (E(DCA)2•–/(2DCA–)) havemore » been determined.« less

Authors:

Das, Laboni ^[1]; Kumar, Rahul ^[2];

^[2];

^[3]; Dhiman, Surajdevprakash B. ^[4];

^[4]

Bhabha Atomic Research Centre, Mumbai (India). Radiation & Photochemistry Division; Homi Bhabha National Inst., Anushaktinagar, Mumbai (India).
Homi Bhabha National Inst., Anushaktinagar, Mumbai (India).
Bhabha Atomic Research Centre, Mumbai (India). Radiation & Photochemistry Division
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division

Publication Date:: 2018-03-06

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States)

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

OSTI Identifier:: 1433984

Report Number(s):: BNL-203525-2018-JAAM
Journal ID: ISSN 1089-5639; TRN: US1802548

Grant/Contract Number:: SC0012704

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Additional Journal Information:: Journal Volume: 122; Journal Issue: 12; Journal ID: ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ionic liquids; radiation chemistry

Citation Formats


                    Das, Laboni, Kumar, Rahul, Maity, Dilip K., Adhikari, Soumyakanti, Dhiman, Surajdevprakash B., and Wishart, James F. Pulse Radiolysis and Computational Studies on a Pyrrolidinium Dicyanamide Ionic Liquid: Detection of the Dimer Radical Anion.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpca.8b00978.

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                    Das, Laboni, Kumar, Rahul, Maity, Dilip K., Adhikari, Soumyakanti, Dhiman, Surajdevprakash B., & Wishart, James F. Pulse Radiolysis and Computational Studies on a Pyrrolidinium Dicyanamide Ionic Liquid: Detection of the Dimer Radical Anion.  United States.  https://doi.org/10.1021/acs.jpca.8b00978

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                    Das, Laboni, Kumar, Rahul, Maity, Dilip K., Adhikari, Soumyakanti, Dhiman, Surajdevprakash B., and Wishart, James F. Tue .  
"Pulse Radiolysis and Computational Studies on a Pyrrolidinium Dicyanamide Ionic Liquid: Detection of the Dimer Radical Anion".  United States.  https://doi.org/10.1021/acs.jpca.8b00978.  https://www.osti.gov/servlets/purl/1433984.

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@article{osti_1433984,

  title        = {Pulse Radiolysis and Computational Studies on a Pyrrolidinium Dicyanamide Ionic Liquid: Detection of the Dimer Radical Anion},

  author       = {Das, Laboni and Kumar, Rahul and Maity, Dilip K. and Adhikari, Soumyakanti and Dhiman, Surajdevprakash B. and Wishart, James F.},

  abstractNote = {A pulse radiolysis study on pyrrolidinium cation based ionic liquids is presented here in this paper. Time-resolved absorption spectra for 1-methyl-1-propylpyrrolidinium dicyanamide (DCA) at 500 ns after the electron pulse show broad absorption bands at wavelengths below 440 nm and at 640 nm. In pyrrolidinium bis(trifluoromethylsulfonyl)imide (NTf2) and tris(perfluoroethyl)trifluorophosphate (FAP) ILs, the transient absorption below 440 nm is much weaker. The absorption at 500 ns, which increases with wavelength from 500 nm to beyond 800 nm, was assigned to the tail of the solvated electron NIR absorption spectrum, since it disappears in the presence of N2O. In the DCA IL, the presence of a reducing species was confirmed by the formation of pyrene radical anion. The difference in the transient species in the case of the DCA IL compared to other two ILs should be due to the anion, with cations being similar. In pseudohalide ILs such as DCA, radicals are formed by direct hole trapping by the anion (X– + h+ → X•), followed by addition to the parent anion. Prediction of the UV/vis absorption spectra of the dimer radical anion by computational calculation supports the experimental results. The oxidizing efficiency of (DCA)2•– and its reduction potential (E(DCA)2•–/(2DCA–)) have been determined.},

  doi          = {10.1021/acs.jpca.8b00978},

  journal      = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},

  number       = 12,

  volume       = 122,

  place        = {United States},

  year         = {2018},

  month        = {3}

}

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