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Title: Identification of ion-pair structures in solution by vibrational stark effects

Abstract

Here, ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N) infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show thatmore » a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.« less

Authors:
 [1];  [2];  [2];  [2]
+ Show Author Affiliations
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. of Virginia, Charlottesville, VA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1247984
Report Number(s):
BNL-112077-2016-JA
Journal ID: ISSN 1520-6106; R&D Project: CO004; KC0304030
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 120; Journal Issue: 6; 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

Hack, John, Mani, Tomoyasu, Grills, David C., and Miller, John R. Identification of ion-pair structures in solution by vibrational stark effects. United States: N. p., 2016. Web. doi:10.1021/acs.jpcb.5b11893.
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Hack, John, Mani, Tomoyasu, Grills, David C., & Miller, John R. Identification of ion-pair structures in solution by vibrational stark effects. United States. https://doi.org/10.1021/acs.jpcb.5b11893
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Hack, John, Mani, Tomoyasu, Grills, David C., and Miller, John R. Mon . "Identification of ion-pair structures in solution by vibrational stark effects". United States. https://doi.org/10.1021/acs.jpcb.5b11893. https://www.osti.gov/servlets/purl/1247984.
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@article{osti_1247984,
title = {Identification of ion-pair structures in solution by vibrational stark effects},
author = {Hack, John and Mani, Tomoyasu and Grills, David C. and Miller, John R.},
abstractNote = {Here, ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N) infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.},
doi = {10.1021/acs.jpcb.5b11893},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 6,
volume = 120,
place = {United States},
year = {Mon Jan 25 00:00:00 EST 2016},
month = {Mon Jan 25 00:00:00 EST 2016}
}
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Works referenced in this record:

Ions and ion pairs
journal, March 1969

Structure of Ion Pair Solvation Complexes
journal, February 1972

  • Smid, Johannes
  • Angewandte Chemie International Edition in English, Vol. 11, Issue 2
  • DOI: 10.1002/anie.197201121

Ion Pairing
journal, November 2006

  • Marcus, Yizhak; Hefter, Glenn
  • Chemical Reviews, Vol. 106, Issue 11
  • DOI: 10.1021/cr040087x

Electrostatic stabilization in non-aqueous media
journal, October 1992

Ionic Association. III. The Equilibrium between Ion Pairs and Free Ions
journal, October 1958

  • Fuoss, Raymond M.
  • Journal of the American Chemical Society, Vol. 80, Issue 19
  • DOI: 10.1021/ja01552a016

Salt Effects and Ion Pairs in Solvolysis and Related Reactions. III. 1 Common Ion Rate Depression and Exchange of Anions during Acetolysis 2,3
journal, January 1956

  • Winstein, S.; Clippinger, E.; Fainberg, A. H.
  • Journal of the American Chemical Society, Vol. 78, Issue 2
  • DOI: 10.1021/ja01583a022

Electrolyte-solvent Interaction. IV. Tetrabutylammonium Bromide in Methanol-Carbon Tetrachloride and Methanol-Heptane Mixtures
journal, December 1954

  • Sadek, Hussein; Fuoss, Raymond M.
  • Journal of the American Chemical Society, Vol. 76, Issue 23
  • DOI: 10.1021/ja01652a001

Dynamics of Radical Ion Pairs following Photoinduced Electron Transfer in Solvents with Low and Intermediate Polarities
journal, December 2014

  • Mentel, Kamila K.; Nunes, Rui M. D.; Serpa, Carlos
  • The Journal of Physical Chemistry B, Vol. 119, Issue 24
  • DOI: 10.1021/jp511425y

Investigations of bimolecular photoinduced electron transfer reactions in polar solvents using ultrafast spectroscopy
journal, April 2006

Interpretation of Data Obtained in Nonaqueous Media
journal, November 1954

Studies of Contact and Solvent-Separated Ion Pairs of Carbanions. I. Effect of Temperature, Counterion, and Solvent
journal, January 1966

  • Esch, T. E. Hogen-; Smid, J.
  • Journal of the American Chemical Society, Vol. 88, Issue 2
  • DOI: 10.1021/ja00954a024

Equilibrium of Contact and Solvent-Separated Ion Pairs in Mixtures of Protic Ionic Liquids and Molecular Solvents Controlled by Polarity
journal, October 2013

  • Fumino, Koichi; Stange, Peter; Fossog, Verlaine
  • Angewandte Chemie International Edition, Vol. 52, Issue 47
  • DOI: 10.1002/anie.201303944

Ion Pairing in Protic Ionic Liquids Probed by Far-Infrared Spectroscopy: Effects of Solvent Polarity and Temperature
journal, June 2014

Vibrational Stark Effects To Identify Ion Pairing and Determine Reduction Potentials in Electrolyte-Free Environments
journal, January 2015

  • Mani, Tomoyasu; Grills, David C.; Miller, John R.
  • Journal of the American Chemical Society, Vol. 137, Issue 3
  • DOI: 10.1021/ja512302c

Development of nanosecond time-resolved infrared detection at the LEAF pulse radiolysis facility
journal, April 2015

  • Grills, David C.; Farrington, Jaime A.; Layne, Bobby H.
  • Review of Scientific Instruments, Vol. 86, Issue 4
  • DOI: 10.1063/1.4918728

The LEAF picosecond pulse radiolysis facility at Brookhaven National Laboratory
journal, November 2004

  • Wishart, James F.; Cook, Andrew R.; Miller, John R.
  • Review of Scientific Instruments, Vol. 75, Issue 11
  • DOI: 10.1063/1.1807004

Stark Realities †
journal, March 2009

  • Boxer, Steven G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 10
  • DOI: 10.1021/jp8067393

Measuring Electric Fields and Noncovalent Interactions Using the Vibrational Stark Effect
journal, March 2015

  • Fried, Stephen D.; Boxer, Steven G.
  • Accounts of Chemical Research, Vol. 48, Issue 4
  • DOI: 10.1021/ar500464j

Understanding and Manipulating Electrostatic Fields at the Protein–Protein Interface Using Vibrational Spectroscopy and Continuum Electrostatics Calculations
journal, October 2015

  • Ritchie, Andrew W.; Webb, Lauren J.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 44
  • DOI: 10.1021/acs.jpcb.5b06888

Benzonitrile as a Probe of Local Environment in Ionic Liquids
journal, February 2013

  • Zhang, Shiguo; Zhang, Yan; Ma, Xiangyuan
  • The Journal of Physical Chemistry B, Vol. 117, Issue 9
  • DOI: 10.1021/jp312251q

Thiocyanate as a Local Probe of Ultrafast Structure and Dynamics in Imidazolium-Based Ionic Liquids: Water-Induced Heterogeneity and Cation-Induced Ion Pairing
journal, March 2015

  • Ren, Zhe; Brinzer, Thomas; Dutta, Samrat
  • The Journal of Physical Chemistry B, Vol. 119, Issue 13
  • DOI: 10.1021/jp512851v

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

  • Ren, Zhe; Ivanova, Anna S.; Couchot-Vore, Duane
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 9
  • DOI: 10.1021/jz500372f

Vibrational Stark Effects of Nitriles I. Methods and Experimental Results
journal, December 2000

  • Andrews, Steven S.; Boxer, Steven G.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 51
  • DOI: 10.1021/jp002242r

Ultrafast Vibrational Stark-Effect Spectroscopy: Exploring Charge-Transfer Reactions by Directly Monitoring the Solvation Shell Response
journal, September 2010

  • Baiz, Carlos R.; Kubarych, Kevin J.
  • Journal of the American Chemical Society, Vol. 132, Issue 37
  • DOI: 10.1021/ja1043853

Ion-pairing dynamics of Li + and SCN − in dimethylformamide solution: Chemical exchange two-dimensional infrared spectroscopy
journal, February 2011

  • Lee, Kyung-Koo; Park, Kwang-Hee; Kwon, Donghyun
  • The Journal of Chemical Physics, Vol. 134, Issue 6
  • DOI: 10.1063/1.3552961

Real‐Time Probing of Ion Pairing Dynamics with 2DIR Spectroscopy
journal, November 2010

  • Park, Kwang‐Hee; Choi, Seung Ryul; Choi, Jun‐Ho
  • ChemPhysChem, Vol. 11, Issue 17
  • DOI: 10.1002/cphc.201000595

Solute-solute interactions in liquid ammonia solutions: a vibrational spectroscopic view
journal, January 1981

Electron Localization of Anions Probed by Nitrile Vibrations
journal, August 2015

  • Mani, Tomoyasu; Grills, David C.; Newton, Marshall D.
  • Journal of the American Chemical Society, Vol. 137, Issue 34
  • DOI: 10.1021/jacs.5b04648

Synthesis and properties of crown ether-modified phosphines and their use as ligands in transition metal catalysts
journal, May 1988

  • Okano, Tamon; Iwahara, Masahiro; Konishi, Hisatoshi
  • Journal of Organometallic Chemistry, Vol. 346, Issue 2
  • DOI: 10.1016/0022-328X(88)80123-2

Establishment of an Efficient Synthetic Route to 3,4:3’,4’-Bis(3,6,9-trioxaundecane-1,11-dioxy)benzil
journal, January 2006

  • Kimura, Masaru; Shi, Kun; Hashimoto, Koji
  • HETEROCYCLES, Vol. 68, Issue 11
  • DOI: 10.3987/COM-06-10831

Tests of functionals for systems with fractional electron number
journal, April 2007

  • Vydrov, Oleg A.; Scuseria, Gustavo E.; Perdew, John P.
  • The Journal of Chemical Physics, Vol. 126, Issue 15
  • DOI: 10.1063/1.2723119

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009

Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model
journal, April 2003

  • Cossi, Maurizio; Rega, Nadia; Scalmani, Giovanni
  • Journal of Computational Chemistry, Vol. 24, Issue 6
  • DOI: 10.1002/jcc.10189

Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model
journal, March 1998

  • Barone, Vincenzo; Cossi, Maurizio
  • The Journal of Physical Chemistry A, Vol. 102, Issue 11
  • DOI: 10.1021/jp9716997

Solvent-Induced Infrared Frequency Shifts in Aromatic Nitriles Are Quantitatively Described by the Vibrational Stark Effect
journal, April 2012

  • Levinson, Nicholas M.; Fried, Stephen D.; Boxer, Steven G.
  • The Journal of Physical Chemistry B, Vol. 116, Issue 35
  • DOI: 10.1021/jp301054e

The Chemistry of the Radical Anion of Tetraphenylethylene
journal, December 1965

  • Roberts, R. C.; Szwarc, M.
  • Journal of the American Chemical Society, Vol. 87, Issue 24
  • DOI: 10.1021/ja00952a004

Ionic radii from scaled particle theory of the salt effect
journal, September 1971

  • Masterton, W. L.; Bolocofsky, David; Lee, Tei Pei
  • The Journal of Physical Chemistry, Vol. 75, Issue 18
  • DOI: 10.1021/j100687a017

Tetraalkylammonium Ions in Aqueous and Non-aqueous Solutions
journal, June 2008

Penetrated Ion Pairs: a New Form of Ion Pair
journal, June 1992

  • Boche, Gernot
  • Angewandte Chemie International Edition in English, Vol. 31, Issue 6
  • DOI: 10.1002/anie.199207311

Penetrated ion pairs: photochemistry of cyanine dyes within organic borates
journal, January 1992

  • Yang, Xiqiang; Zaitsev, Alexei; Sauerwein, Bjorn
  • Journal of the American Chemical Society, Vol. 114, Issue 2
  • DOI: 10.1021/ja00028a075

Electrochemistry in media of low dielectric constant
journal, January 1993

Crystallographic Distinction between “Contact” and “Separated” Ion Pairs:  Structural Effects on Electronic/ESR Spectra of Alkali-Metal Nitrobenzenides
journal, April 2004

  • Davlieva, Milya G.; Lü, Jian-Ming; Lindeman, Sergey V.
  • Journal of the American Chemical Society, Vol. 126, Issue 14
  • DOI: 10.1021/ja049856k

Quinones as Electron Acceptors. X-Ray Structures, Spectral (EPR, UV−vis) Characteristics and Electron-Transfer Reactivities of Their Reduced Anion Radicals as Separated vs Contact Ion Pairs
journal, December 2006

  • Lü, Jian-Ming; Rosokha, Sergiy V.; Neretin, Ivan S.
  • Journal of the American Chemical Society, Vol. 128, Issue 51
  • DOI: 10.1021/ja066471o

“Separated” versus “Contact” Ion-Pair Structures in Solution from Their Crystalline States:  Dynamic Effects on Dinitrobenzenide as a Mixed-Valence Anion
journal, February 2005

  • Lü, Jian-Ming; Rosokha, Sergiy V.; Lindeman, Sergey V.
  • Journal of the American Chemical Society, Vol. 127, Issue 6
  • DOI: 10.1021/ja043998x

Tetraalkylammonium ions are surrounded by an inner solvation shell in strong electron pair donor solvents
journal, February 2009

Reduction Potentials of One‐Electron Couples Involving Free Radicals in Aqueous Solution
journal, October 1989

  • Wardman, Peter
  • Journal of Physical and Chemical Reference Data, Vol. 18, Issue 4
  • DOI: 10.1063/1.555843

One-Electron and Two-Electron Transfers in Electrochemistry and Homogeneous Solution Reactions
journal, July 2008

Effect of Ion Pairing on the Mechanism and Rate of Electron Transfer. Electrochemical Aspects
journal, August 2001

  • Savéant, Jean-Michel
  • The Journal of Physical Chemistry B, Vol. 105, Issue 37
  • DOI: 10.1021/jp011374x

Role of Bad Dihedral Angles: Methylfluorenes Act as Energy Barriers for Excitons and Polarons of Oligofluorenes
journal, September 2014

  • Mani, Tomoyasu; Miller, John R.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 40
  • DOI: 10.1021/jp5080626

Electronic Structure and Optical Properties of Charged Oligofluorenes Studied by VIS/NIR Spectroscopy and Time-Dependent Density Functional Theory
journal, March 2006

  • Fratiloiu, Silvia; Grozema, Ferdinand C.; Koizumi, Yoshiko
  • The Journal of Physical Chemistry B, Vol. 110, Issue 12
  • DOI: 10.1021/jp055785f

Cyclic polyethers and their complexes with metal salts
journal, May 1967

  • Pedersen, Charles J.
  • Journal of the American Chemical Society, Vol. 89, Issue 10
  • DOI: 10.1021/ja00986a052

Cyclic polyethers and their complexes with metal salts
journal, December 1967

  • Pedersen, Charles J.
  • Journal of the American Chemical Society, Vol. 89, Issue 26
  • DOI: 10.1021/ja01002a035

Crown Ethers:  Sensors for Ions and Molecular Scaffolds for Materials and Biological Models
journal, May 2004

  • Gokel, George W.; Leevy, W. Matthew; Weber, Michelle E.
  • Chemical Reviews, Vol. 104, Issue 5
  • DOI: 10.1021/cr020080k
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