Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: IR linewidth and intensity amplifications of nitrile vibrations report nuclear-electronic couplings and associated structural heterogeneity in radical anions

Abstract

Conjugated molecular chains have the potential to act as “molecular wires” that can be employed in a variety of technologies, including catalysis, molecular electronics, and quantum information technologies. Their successful application relies on a detailed understanding of the factors governing the electronic energy landscape and the dynamics of electrons in such molecules. We can gain insights into the energetics and dynamics of charges in conjugated molecules using time-resolved infrared (TRIR) detection combined with pulse radiolysis. Nitrile ν(CN) bands can act as IR probes for charges, based on IR frequency shifts, because of their exquisite sensitivity to the degree of electron delocalization and induced electric field. Here, we show that the IR intensity and linewidth can also provide unique and complementary information on the nature of charges. Quantifications of IR intensity and linewidth in a series of nitrile-functionalized oligophenylenes reveal that the CN vibration is coupled to the nuclear and electronic structural changes, which become more prominent when an excess charge is present. We synthesized a new series of ladder-type oligophenylenes that possess planar aromatic structures, as revealed by X-ray crystallography. Using these, we demonstrate that CN vibrations can report charge fluctuations associated with nuclear movements, namely those driven by motionsmore » of flexible dihedral angles. This happens only when a charge has room to fluctuate in space.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]
+ Show Author Affiliations
  1. Department of Physical Sciences, Eastern New Mexico University, Portales, NM 88130, USA
  2. Department of Chemistry, University of Connecticut, Storrs, CT 06269-3060, USA
  3. Chemistry Division, Brookhaven National Laboratory, Upton, NY 11973-5000, USA
  4. Rigaku Americas Corporation, 9009 New Trails Drive, The Woodlands, TX 77381, USA
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1813631
Alternate Identifier(s):
OSTI ID: 1813956
Report Number(s):
BNL-222008-2021-JAAM
Journal ID: ISSN 2041-6520; CSHCBM
Grant/Contract Number:  
SC0012704
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 12 Journal Issue: 36; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Yan, Juchao, Wilson, Reid W., Buck, Jason T., Grills, David C., Reinheimer, Eric W., and Mani, Tomoyasu. IR linewidth and intensity amplifications of nitrile vibrations report nuclear-electronic couplings and associated structural heterogeneity in radical anions. United Kingdom: N. p., 2021. Web. doi:10.1039/D1SC03455C.
Copy to clipboard
Yan, Juchao, Wilson, Reid W., Buck, Jason T., Grills, David C., Reinheimer, Eric W., & Mani, Tomoyasu. IR linewidth and intensity amplifications of nitrile vibrations report nuclear-electronic couplings and associated structural heterogeneity in radical anions. United Kingdom. https://doi.org/10.1039/D1SC03455C
Copy to clipboard
Yan, Juchao, Wilson, Reid W., Buck, Jason T., Grills, David C., Reinheimer, Eric W., and Mani, Tomoyasu. Wed . "IR linewidth and intensity amplifications of nitrile vibrations report nuclear-electronic couplings and associated structural heterogeneity in radical anions". United Kingdom. https://doi.org/10.1039/D1SC03455C.
Copy to clipboard
@article{osti_1813631,
title = {IR linewidth and intensity amplifications of nitrile vibrations report nuclear-electronic couplings and associated structural heterogeneity in radical anions},
author = {Yan, Juchao and Wilson, Reid W. and Buck, Jason T. and Grills, David C. and Reinheimer, Eric W. and Mani, Tomoyasu},
abstractNote = {Conjugated molecular chains have the potential to act as “molecular wires” that can be employed in a variety of technologies, including catalysis, molecular electronics, and quantum information technologies. Their successful application relies on a detailed understanding of the factors governing the electronic energy landscape and the dynamics of electrons in such molecules. We can gain insights into the energetics and dynamics of charges in conjugated molecules using time-resolved infrared (TRIR) detection combined with pulse radiolysis. Nitrile ν(CN) bands can act as IR probes for charges, based on IR frequency shifts, because of their exquisite sensitivity to the degree of electron delocalization and induced electric field. Here, we show that the IR intensity and linewidth can also provide unique and complementary information on the nature of charges. Quantifications of IR intensity and linewidth in a series of nitrile-functionalized oligophenylenes reveal that the CN vibration is coupled to the nuclear and electronic structural changes, which become more prominent when an excess charge is present. We synthesized a new series of ladder-type oligophenylenes that possess planar aromatic structures, as revealed by X-ray crystallography. Using these, we demonstrate that CN vibrations can report charge fluctuations associated with nuclear movements, namely those driven by motions of flexible dihedral angles. This happens only when a charge has room to fluctuate in space.},
doi = {10.1039/D1SC03455C},
journal = {Chemical Science},
number = 36,
volume = 12,
place = {United Kingdom},
year = {Wed Sep 22 00:00:00 EDT 2021},
month = {Wed Sep 22 00:00:00 EDT 2021}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/D1SC03455C
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Assessment of a long-range corrected hybrid functional
journal, December 2006

  • Vydrov, Oleg A.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 125, Issue 23
  • DOI: 10.1063/1.2409292

Probing and Exploiting the Interplay between Nuclear and Electronic Motion in Charge Transfer Processes
journal, March 2015

  • Delor, Milan; Sazanovich, Igor V.; Towrie, Michael
  • Accounts of Chemical Research, Vol. 48, Issue 4
  • DOI: 10.1021/ar500420c

Nitrile Vibration Reports Induced Electric Field and Delocalization of Electron in the Charge-Transfer State of Aryl Nitriles
journal, August 2018

  • Mani, Tomoyasu; Grills, David C.
  • The Journal of Physical Chemistry A, Vol. 122, Issue 37
  • DOI: 10.1021/acs.jpca.8b08025

Chain Length Dependence of Energies of Electron and Triplet Polarons in Oligofluorenes
journal, March 2017

  • Chen, Hung Cheng; Sreearunothai, Paiboon; Cook, Andrew R.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 11
  • DOI: 10.1021/acs.jpcc.7b00099

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

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

Delocalisation softens polaron electronic transitions and vibrational modes in conjugated polymers
journal, January 2018

  • Kahmann, Simon; Loi, Maria A.; Brabec, Christoph J.
  • Journal of Materials Chemistry C, Vol. 6, Issue 22
  • DOI: 10.1039/C8TC00909K

Vibrational Probes: From Small Molecule Solvatochromism Theory and Experiments to Applications in Complex Systems
journal, February 2017

The CN Stretching Band of Aliphatic Thiocyanate is Sensitive to Solvent Dynamics and Specific Solvation
journal, October 2007

  • Maienschein-Cline, Mark G.; Londergan, Casey H.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 40
  • DOI: 10.1021/jp0761158

Vibrational Excitations of Charged Solitons in Polyacetylene
journal, September 1980

Role of solvent on vibrational energy transfer in solution
journal, October 1990

  • Bakker, H. J.; Planken, P. C. M.; Lagendijk, A.
  • Nature, Vol. 347, Issue 6295
  • DOI: 10.1038/347745a0

Exploiting chemistry and molecular systems for quantum information science
journal, July 2020

  • Wasielewski, Michael R.; Forbes, Malcolm D. E.; Frank, Natia L.
  • Nature Reviews Chemistry, Vol. 4, Issue 9
  • DOI: 10.1038/s41570-020-0200-5

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

First-Principles Study of the Nuclear Dynamics of Doped Conjugated Polymers
journal, January 2016

  • Yin, Jun; Wang, Zilong; Fazzi, Daniele
  • The Journal of Physical Chemistry C, Vol. 120, Issue 3
  • DOI: 10.1021/acs.jpcc.5b11764

Structural Effects on Nitrile Infrared Integrated Intensities of Alpha,Beta-Diaryl Cyanoethylenes: Hammett and Quantum Chemical Approaches
journal, May 1978

  • Juchnovski, Ivan; Kuzmanova, Rositza; Tsenov, Jordan
  • Zeitschrift für Naturforschung B, Vol. 33, Issue 5
  • DOI: 10.1515/znb-1978-0518

On the mechanism of vibrational control of light-induced charge transfer in donor–bridge–acceptor assemblies
journal, August 2015

  • Delor, Milan; Keane, Theo; Scattergood, Paul A.
  • Nature Chemistry, Vol. 7, Issue 9
  • DOI: 10.1038/nchem.2327

Tunable Redox Potential, Optical Properties, and Enhanced Stability of Modified Ferrocene-Based Complexes
journal, September 2019

Charge Photogeneration in Organic Solar Cells
journal, November 2010

  • Clarke, Tracey M.; Durrant, James R.
  • Chemical Reviews, Vol. 110, Issue 11, p. 6736-6767
  • DOI: 10.1021/cr900271s

Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects
journal, February 2016

  • Hack, John; Grills, David C.; Miller, John R.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 6
  • DOI: 10.1021/acs.jpcb.5b11893

OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009

  • Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
  • Journal of Applied Crystallography, Vol. 42, Issue 2
  • DOI: 10.1107/S0021889808042726

Ultrafast photoinduced charge generation in conjugated polymers
journal, January 2000

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

Stark Realities †
journal, March 2009

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

Toward control of electron transfer in donor-acceptor molecules by bond-specific infrared excitation
journal, December 2014

  • Delor, Milan; Scattergood, Paul A.; Sazanovich, Igor V.
  • Science, Vol. 346, Issue 6216
  • DOI: 10.1126/science.1259995

Infrared-active vibrational modes of charged solitons in ( CH ) x and ( CD ) x
journal, May 1981

Modulating Unimolecular Charge Transfer by Exciting Bridge Vibrations
journal, December 2009

  • Lin, Zhiwei; Lawrence, Candace M.; Xiao, Dequan
  • Journal of the American Chemical Society, Vol. 131, Issue 50
  • DOI: 10.1021/ja907041t

SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053273314026370

Microscopic insights into the protein-stabilizing effect of trimethylamine N-oxide (TMAO)
journal, May 2014

  • Ma, J.; Pazos, I. M.; Gai, F.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 23
  • DOI: 10.1073/pnas.1403224111

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

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

Vibrational Spectroscopic Map, Vibrational Spectroscopy, and Intermolecular Interaction
journal, June 2020

Using Nitrile-Derivatized Amino Acids as Infrared Probes of Local Environment
journal, January 2003

  • Getahun, Zelleka; Huang, Cheng-Yen; Wang, Ting
  • Journal of the American Chemical Society, Vol. 125, Issue 2
  • DOI: 10.1021/ja0285262

Infrared Probes Based on Nitrile-Derivatized Prolines: Thermal Insulation Effect and Enhanced Dynamic Range
journal, June 2013

  • Park, Kwang-Hee; Jeon, Jonggu; Park, Yumi
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 13
  • DOI: 10.1021/jz400954r

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

Stark Tuning Rates of Organic Carbonates Used in Electrochemical Energy Storage Devices
journal, April 2019

  • Olson, Jarred Z.; Schneider, Samuel H.; Johansson, Patrik K.
  • The Journal of Physical Chemistry C, Vol. 123, Issue 18
  • DOI: 10.1021/acs.jpcc.9b01501

Infrared Activity of Symmetric Bridging Ligand Modes in Pyrazine-Bridged Hexaruthenium Mixed-Valence Clusters
journal, February 2003

  • Londergan, Casey H.; Salsman, J. Catherine; Ronco, Silvia
  • Inorganic Chemistry, Vol. 42, Issue 4
  • DOI: 10.1021/ic0261629

Infrared spectra and structures of carbanions—XI
journal, January 1977

Structure validation in chemical crystallography
journal, January 2009

  • Spek, Anthony L.
  • Acta Crystallographica Section D Biological Crystallography, Vol. 65, Issue 2, p. 148-155
  • DOI: 10.1107/S090744490804362X

Intensity of the carbonyl stretching modes in certain halogenocarbonyl derivatives of chromium, tungsten, manganese, rhenium and iron
journal, January 1967

Theory of Vibrational Circular Dichroism and Infrared Absorption:  Extension to Molecules with Low-Lying Excited Electronic States
journal, September 2004

  • Nafie, Laurence A.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 35
  • DOI: 10.1021/jp0499124

The Degree of Charge Transfer in Ground and Charge-Separated States Revealed by Ultrafast Visible Pump/Mid-IR Probe Spectroscopy
journal, April 2004

  • Rubtsov, Igor V.; Kang, Youn K.; Redmore, Naomi P.
  • Journal of the American Chemical Society, Vol. 126, Issue 16
  • DOI: 10.1021/ja030674k

Giant infrared absorption bands of electrons and holes in conjugated molecules
journal, November 2013

  • Zamadar, Matibur; Asaoka, Sadayuki; Grills, David C.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3818

Looking at Photoinduced Charge Transfer Processes in the IR: Answers to Several Long-Standing Questions
journal, January 2017

Synthesis of Methylene-Bridge Polyarenes through Palladium-Catalyzed Activation of Benzylic Carbon-Hydrogen Bond
journal, December 2010

  • Hsiao, Chien-Chi; Lin, Yi-Kuan; Liu, Chia-Ju
  • Advanced Synthesis & Catalysis, Vol. 352, Issue 18
  • DOI: 10.1002/adsc.201000651

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

Conjugation and the Intensity of the Infrared Carbonyl Band
journal, November 1953

  • Barrow, Gordon M.
  • The Journal of Chemical Physics, Vol. 21, Issue 11
  • DOI: 10.1063/1.1698732

Electron-Transfer Acceleration Investigated by Time Resolved Infrared Spectroscopy
journal, February 2015

  • Vlček, Antonín; Kvapilová, Hana; Towrie, Michael
  • Accounts of Chemical Research, Vol. 48, Issue 3
  • DOI: 10.1021/ar5004048

Probing Intermolecular Electron Delocalization in Dimer Radical Anions by Vibrational Spectroscopy
journal, July 2017

  • Mani, Tomoyasu; Grills, David C.
  • The Journal of Physical Chemistry B, Vol. 121, Issue 30
  • DOI: 10.1021/acs.jpcb.7b02559

Infrared signatures of positive and negative charge carriers in conjugated polymers with low band gaps
journal, February 2004

Crystal structure refinement with SHELXL
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218

Electron Affinities of Aromatic Hydrocarbons in Tetrahydrofuran Solution
journal, February 1965

  • Jagur-Grodzinski, J.; Feld, M.; Yang, S. L.
  • The Journal of Physical Chemistry, Vol. 69, Issue 2
  • DOI: 10.1021/j100886a045

Intramolecular vibrational stabilization of the charge density wave state in organic metals
journal, November 1975

Reexamination of the Rehm–Weller Data Set Reveals Electron Transfer Quenching That Follows a Sandros–Boltzmann Dependence on Free Energy
journal, August 2011

  • Farid, Samir; Dinnocenzo, Joseph P.; Merkel, Paul B.
  • Journal of the American Chemical Society, Vol. 133, Issue 30
  • DOI: 10.1021/ja2024367

Quantum Theory of the Intensities of Molecular Vibrational Spectra
journal, February 1970

  • Peticolas, Warner L.; Nafie, Laurence; Stein, Paul
  • The Journal of Chemical Physics, Vol. 52, Issue 3
  • DOI: 10.1063/1.1673170

Synthesis of Ladder Polymers: Developments, Challenges, and Opportunities
journal, September 2017

  • Teo, Yew Chin; Lai, Holden W. H.; Xia, Yan
  • Chemistry - A European Journal, Vol. 23, Issue 57
  • DOI: 10.1002/chem.201702219

Extreme electric fields power catalysis in the active site of ketosteroid isomerase
journal, December 2014

Determination of constants of anionic substituents based on nitrile infrared frequencies and intensities
journal, January 1982

  • Binev, Ivan G.; Kuzmanova, Rositsa B.; Kaneti, Jos�
  • Journal of the Chemical Society, Perkin Transactions 2, Issue 12
  • DOI: 10.1039/p29820001533

Synthesis of Fluorene and Indenofluorene Compounds: Tandem Palladium-Catalyzed Suzuki Cross-Coupling and Cyclization
journal, March 2010

  • Liu, Tao-Ping; Xing, Chun-Hui; Hu, Qiao-Sheng
  • Angewandte Chemie International Edition, Vol. 49, Issue 16
  • DOI: 10.1002/anie.201000327

CN stretching vibration of 5-cyanotryptophan as an infrared probe of protein local environment: what determines its frequency?
journal, January 2016

  • Zhang, Wenkai; Markiewicz, Beatrice N.; Doerksen, Rosalie S.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 10
  • DOI: 10.1039/C5CP04413H

Application of transient infrared and near infrared spectroscopy to transition metal complex excited states and intermediates
journal, February 2007

  • Butler, Jennifer M.; George, Michael W.; Schoonover, Jon R.
  • Coordination Chemistry Reviews, Vol. 251, Issue 3-4
  • DOI: 10.1016/j.ccr.2006.12.002

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

Polarons, Bipolarons, and Side-By-Side Polarons in Reduction of Oligofluorenes
journal, June 2012

  • Zaikowski, Lori; Kaur, Parmeet; Gelfond, Claudia
  • Journal of the American Chemical Society, Vol. 134, Issue 26
  • DOI: 10.1021/ja301494n

Vibrational Spectroscopy Reveals Effects of Electron Push–Pull and Solvent Polarity on Electron Delocalization in Radical Anions of Donor–Acceptor Compounds
journal, February 2020

  • Boudreau, Andrew M.; Wilson, Reid W.; Yang, Mengshijie
  • The Journal of Physical Chemistry B, Vol. 124, Issue 8
  • DOI: 10.1021/acs.jpcb.9b11747

Importance of short-range versus long-range Hartree-Fock exchange for the performance of hybrid density functionals
journal, August 2006

  • Vydrov, Oleg A.; Heyd, Jochen; Krukau, Aliaksandr V.
  • The Journal of Chemical Physics, Vol. 125, Issue 7
  • DOI: 10.1063/1.2244560

Infrared spectral data on strong intramolecular electron interaction in some anion radicals containing CN groups
journal, December 1971

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: