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

Full Record
Other Related Research

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:: Tue Mar 06 00:00:00 EST 2018

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.

Copy to clipboard


                    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

Copy to clipboard


                    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.

Copy to clipboard


                    
@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         = {Tue Mar 06 00:00:00 EST 2018},

  month        = {Tue Mar 06 00:00:00 EST 2018}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jpca.8b00978

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 4 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Dynamics of an excess hole in the 1-methyl-1-butyl-pyrrolidinium dicyanamide ionic-liquid

Journal Article Wu, Fei ; Xu, Changhui ; Margulis, Claudio J. - Journal of Chemical Physics

In a set of recent publications we explored for selected ionic liquids the early stages of excess charge localization and reactivity relevant both to electrochemical and radiation chemistry processes. W explored the dynamics of an excess electron in 1-methyl-1-butyl-pyrrolidinium dicyanamide. When electrons are produced from an ionic liquid, the more elusive hole species are also generated. Depending on the nature of cations and anions and the relative alignment of their electronic states in the condensed phase, the very early hole species can nominally be neutral radicals—if the electron is generated from anions—or doubly charged radical cations if their origin ismore »« less
Cited by 4
https://doi.org/10.1063/1.5009940

Full Text Available
Raman Wavelength Conversion in Ionic Liquids

Journal Article Kupfer, Rotem ; Wang, Furong ; Wishart, James F. ; ... - Physical Review Applied

Here, we explore the use of room-temperature ionic liquids (ILs) as Raman wavelength converters. ILs provide an engineerable framework to design suitable liquids for wavelength conversion over a broad spectral range, through careful selection of the molecular structures of the IL anions and cations so that specific characteristics can be obtained, such as a desirable Raman shift, low Brillouin scattering, and good optical transmission in the pump and Stokes wavelengths. Applying such criteria, we demonstrate that 1-ethyl-3-methylimidazolium dicyanamide (EMIM DCA) is an effective medium for conversion of 532-nm pulses from a Q-switched Nd :YAG laser to 603 nm. This correspondsmore »« less
https://doi.org/10.1103/physrevapplied.19.014052

Full Text Available
Viscosity of 1-Alkyl-1-methylpyrrolidinium Bis(trifluoromethylsulfonyl)imide Ionic Liquids Saturated with Compressed CO ₂

Journal Article C. Morais, Ana Rita ; Shiflett, Mark B. ; Scurto, Aaron M. ; ... - Journal of Chemical and Engineering Data

The viscosity of mixtures of pyrrolidinium-based ionic liquids saturated with compressed CO₂ was measured using a high-pressure viscometer at three different temperatures (298.15, 318.15 and 338.15 K). The high-pressure viscosity of 1-propyl-1-methyl-pyrrolidinium ([C₃C₁pyr]), 1-butyl-1-methyl-pyrrolidinium ([C₄C₁pyr]), and 1-hexyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide ([C₆C₁pyr]) cations with common anion, bis(trifluoromethylsulfonyl)amide ([NTf₂]), was measured up to a maximum CO₂ pressure of 25 MPa. In the temperature range investigated, the viscosity of the ionic liquid/ CO₂ mixture dramatically decreases with increasing of CO₂ pressure up to approximately 7 MPa but the viscosity decrease becomes less significant at higher CO₂ pressures (from 7 to 25 MPa) because the CO₂more »« less
Cited by 8
https://doi.org/10.1021/acs.jced.8b01237

Full Text Available
Anionic Dicyanamide Frameworks as Possible Components of Multifunctional Materials

Journal Article Schlueter, J. A. ; Geiser, U. ; Manson, Jamie L - Journal de Physique IV

The dicyanamide anion, [N(CN){sub 2}]{sup -} (hereafter abbreviated dca), has been shown to be a versatile building block for the assembly of coordination polymers which are components of molecular superconductors, magnets and conducting/magnetic hybrid materials. Significantly different anion topologies have been observed. We report the first study of the use of alkylammonium cations as templates for [M(dca){sub 3}]{sup -} (M = Mn and Ni) anionic networks, including a novel three-dimensional anionic structure in the (Bu{sub 3}NH){sub 4}[Mn{sub 3}(dca){sub 10}] salt. The molecular superconductors with the highest superconducting transition temperature, {kappa}-(ET){sub 2}[Cu(dca)X] [X = Cl, Br; ET, commonly abbreviated as BEDT-TTF,more »« less
https://doi.org/10.1051/jp4:2004114111
High-Pressure Vapor-Liquid Equilibria of 1-Alkyl-1-Methylpyrrolidinium Bis(trifluoromethylsulfonyl)imide Ionic Liquids and CO ₂

Journal Article Turnaoglu, Tugba ; Minnick, David L. ; Morais, Ana Rita C. ; ... - Journal of Chemical and Engineering Data

The high-pressure vapor-liquid equilibrium for the binary systems of carbon dioxide (CO₂) and a series of 1-alkyl-1-methyl pyrrolidinium bis(trifluoromethylsulfonyl)amide ionic liquids ([C_nC₁pyr][NTf₂] (n = 3,4,6)) are reported at 298.15, 318.15 and 338.15 K and at pressures up to 20 MPa. Experiments were conducted using gravimetric (IGA and XEMIS microbalances) and a volumetric method (high-pressure view cell). The solubility of CO₂ in pyrrolidinium ionic liquids increases with decreasing temperature and increasing pressure. The CO₂ solubility also slightly increases with increase in alkyl chain length on the pyrrolidinium cation. Molar volume and volume expansion of CO₂ + IL mixtures are also reported.more »« less
Cited by 9
https://doi.org/10.1021/acs.jced.8b01236

Full Text Available

Similar Records