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Title: Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids

Abstract

Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyano-borate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients and time-integrated spectra. Finally, application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V0, where D is the relative diffusion coefficient between donor and acceptor and V0 is the value of the electronic coupling at donor-acceptor contact.

Authors:
 [1];  [1];  [2];  [1]
  1. Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 610 Taylor Road, Piscataway, New Jersey 08854, United States
  2. Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
Publication Date:
Research Org.:
Rutgers Univ., Piscataway, NJ (United States); Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1248414
Alternate Identifier(s):
OSTI ID: 1434921
Grant/Contract Number:  
SC0001780; SC0008640
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of Physical Chemistry. B
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. B Journal Volume: 119 Journal Issue: 46; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wu, Boning, Liang, Min, Maroncelli, Mark, and Castner, Jr., Edward W. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids. United States: N. p., 2015. Web. doi:10.1021/acs.jpcb.5b09216.
Wu, Boning, Liang, Min, Maroncelli, Mark, & Castner, Jr., Edward W. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids. United States. https://doi.org/10.1021/acs.jpcb.5b09216
Wu, Boning, Liang, Min, Maroncelli, Mark, and Castner, Jr., Edward W. 2015. "Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids". United States. https://doi.org/10.1021/acs.jpcb.5b09216.
@article{osti_1248414,
title = {Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids},
author = {Wu, Boning and Liang, Min and Maroncelli, Mark and Castner, Jr., Edward W.},
abstractNote = {Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyano-borate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients and time-integrated spectra. Finally, application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V0, where D is the relative diffusion coefficient between donor and acceptor and V0 is the value of the electronic coupling at donor-acceptor contact.},
doi = {10.1021/acs.jpcb.5b09216},
url = {https://www.osti.gov/biblio/1248414}, journal = {Journal of Physical Chemistry. B},
issn = {1520-6106},
number = 46,
volume = 119,
place = {United States},
year = {Mon Nov 09 00:00:00 EST 2015},
month = {Mon Nov 09 00:00:00 EST 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1021/acs.jpcb.5b09216

Citation Metrics:
Cited by: 18 works
Citation information provided by
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Works referenced in this record:

Heterogeneity in a room-temperature ionic liquid: Persistent local environments and the red-edge effect
journal, January 2006


Bimolecular Electron Transfer in Ionic Liquids: Are Reaction Rates Anomalously High?
journal, January 2012


Ionic-liquid materials for the electrochemical challenges of the future
journal, July 2009


Outer-sphere electron transfer in polar solvents
journal, July 1980


On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I
journal, May 1956


Electrostatic Free Energy and Other Properties of States Having Nonequilibrium Polarization. I
journal, May 1956


Adiabatic Electron Transfer in a Room-Temperature Ionic Liquid: Reaction Dynamics and Kinetics
journal, October 2009


Electron transfers in chemistry and biology
journal, August 1985


Time-Dependent Rate Coefficients for Diffusion-Influenced Reactions with Centrosymmetric Potentials
journal, March 2005


Viscosity of (C2–C14) 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ionic liquids in an extended temperature range
journal, February 2011


Free Energy of Nonequilibrium Polarization Systems. II. Homogeneous and Electrode Systems
journal, April 1963


1-Ethyl-3-methylimidazolium Based Ionic Liquids Containing Cyano Groups:  Synthesis, Characterization, and Crystal Structure
journal, February 2004


Ionic Liquids at Electrified Interfaces
journal, March 2014


Computer simulation studies of electron transfer parameters for cyanoanthracene/N,N-dimethylaniline solutions
journal, March 2003


Photoelectron transfer from excited-state ruthenium(ii) tris(bipyridyl) to methylviologen in an ionic liquid
journal, January 2000


How Does the Ionic Liquid Organizational Landscape Change when Nonpolar Cationic Alkyl Groups Are Replaced by Polar Isoelectronic Diethers?
journal, January 2013


Electrochemical Reactivity in Room-Temperature Ionic Liquids
journal, July 2008


Theory of diffusion-influenced fluorescence quenching
journal, September 1989


Spurious Observation of the Marcus Inverted Region in Bimolecular Photoinduced Electron Transfer
journal, July 2012


Physical trends and structural features in organic salts of the thiocyanate anion
journal, October 2002


Experimental Evidence of the Relevance of Orientational Correlations in Photoinduced Bimolecular Reactions in Solution
journal, August 2013


Excitation Wavelength Dependence of the Dynamics of Bimolecular Photoinduced Electron Transfer Reactions
journal, April 2014


A Study of the Time-Resolved Fluorescence Spectrum and Red Edge Effect of ANF in a Room-Temperature Ionic Liquid
journal, June 2006


Influence of Diffusion on the Kinetics of Donor−Acceptor Electron Transfer Monitored by the Quenching of Donor Fluorescence
journal, August 2002


Application of 1-ethyl-3-methylimidazolium thiocyanate to the electrolyte of electrochemical double layer capacitors
journal, November 2006


Chemical Dynamics in Condensed Phases
book, April 2006


Electron-Transfer Dynamics for a Donor–Bridge–Acceptor Complex in Ionic Liquids
journal, July 2015


Ionic Liquids in Electrochemical Devices and Processes: Managing Interfacial Electrochemistry
journal, November 2007


Interactions between water and 1-butyl-1-methylpyrrolidinium ionic liquids
journal, August 2015


Molecular volumes and the Stokes-Einstein equation
journal, April 1970


Solvent-Controlled Intramolecular Electron Transfer in Ionic Liquids
journal, May 2011


Exact calculation of the solvation energy of a pair of ions in polar media within the framework of the dielectric continuum model
journal, November 1998


A Comparison of Electron-Transfer Dynamics in Ionic Liquids and Neutral Solvents
journal, February 2012


A Comparative Electrochemical Study of Diffusion in Room Temperature Ionic Liquid Solvents versus Acetonitrile
journal, March 2005


High-Pressure Testing of Heterogeneous Charge Transfer in a Room-Temperature Ionic Liquid:  Evidence for Solvent Dynamic Control
journal, March 2008


Controlling the Outcome of Electron Transfer Reactions in Ionic Liquids
journal, September 2009


Bimolecular Photoinduced Electron Transfer in Imidazolium-Based Room-Temperature Ionic Liquids Is Not Faster than in Conventional Solvents
journal, February 2012


Communication: Unusual structure and transport in ionic liquid-hexane mixtures
journal, March 2015


Lifetimes of Radical Anions of Dicyanoanthracene, Phenazine, and Anthraquinone in the Excited State from the Selective Electron-Transfer Quenching
journal, January 1996


Solute Diffusion in Ionic Liquids, NMR Measurements and Comparisons to Conventional Solvents
journal, September 2013


Energy applications of ionic liquids
journal, January 2009


Ionic Liquids: Structure and Photochemical Reactions
journal, May 2011


Solute–solute spatial distribution in hydrogen bonding liquids probed with time-dependent intermolecular electron transfer
journal, January 2001


Solvent as Electron Donor:  Donor/Acceptor Electronic Coupling Is a Dynamical Variable
journal, March 2000


Ultrafast Structure and Dynamics in Ionic Liquids: 2D-IR Spectroscopy Probes the Molecular Origin of Viscosity
journal, April 2014


Photoinduced Intermolecular Electron Transfer in Liquid Solutions
journal, July 2004


Structure of 1-Alkyl-1-methylpyrrolidinium Bis(trifluoromethylsulfonyl)amide Ionic Liquids with Linear, Branched, and Cyclic Alkyl Groups
journal, July 2013


Dynamic solvent effects on outer‐sphere electron transfer
journal, August 1987


On the Coherent Description of Diffusion-Influenced Fluorescence Quenching Experiments II: Early Events
journal, February 2010


Ultrafast Photochemistry in Liquids
journal, April 2013


Comparison of Diffusivity Data Derived from Electrochemical and NMR Investigations of the SeCN¯/(SeCN) 2 /(SeCN) 3 ¯ System in Ionic Liquids
journal, June 2011


Electrochemical Stability of Imidazolium Based Ionic Liquids Containing Cyano Groups in the Anion: A Cyclic Voltammetry, XPS and DFT Study
journal, January 2012


A Solvent-Free, SeCN - /(SeCN) 3 - Based Ionic Liquid Electrolyte for High-Efficiency Dye-Sensitized Nanocrystalline Solar Cells
journal, June 2004


Low viscosity ionic liquids based on organic salts of the dicyanamide anion
journal, January 2001


Ionic Liquids Based on Polynitrile Anions: Hydrophobicity, Low Proton Affinity, and High Radiolytic Resistance Combined
journal, May 2013


Fast Calculation of van der Waals Volume as a Sum of Atomic and Bond Contributions and Its Application to Drug Compounds
journal, September 2003


Physicochemical Properties and Structures of Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in Imidazolium Cation
journal, April 2005


Cation/Anion Associations in Ionic Liquids Modulated by Hydration and Ionic Medium
journal, April 2011


Complete Solvation Response of Coumarin 153 in Ionic Liquids
journal, August 2012


Photoinduced intermolecular electron transfer in complex liquids: Experiment and theory
journal, December 2000


Distance Dependence of Electron Transfer in DNA:  The Role of the Reorganization Energy and Free Energy
journal, December 2000


Photoinduced Electron Transfer Reaction in Room Temperature Ionic Liquids:  A Combined Laser Flash Photolysis and Fluorescence Study
journal, March 2007


A subpicosecond, subnanosecond and steady‐state study of diffusion‐influenced fluorescence quenching
journal, July 1990