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Title: Extreme electron polaron spatial delocalization in π-conjugated materials

Abstract

The electron polaron, a spin-1/2 excitation, is the fundamental negative charge carrier in π-conjugated organic materials. Large polaron spatial dimensions result from weak electron-lattice coupling and thus identify materials with unusually low barriers for the charge transfer reactions that are central to electronic device applications. In this paper, we demonstrate electron polarons in π-conjugated multiporphyrin arrays that feature vast areal delocalization. This finding is evidenced by concurrent optical and electron spin resonance measurements, coupled with electronic structure calculations that suggest atypically small reorganization energies for one-electron reduction of these materials. Finally, because the electron polaron dimension can be linked to key performance metrics in organic photovoltaics, light-emitting diodes, and a host of other devices, these findings identify conjugated materials with exceptional optical, electronic, and spintronic properties.

Authors:
 [1];  [2];  [3]
  1. Duke Univ., Durham, NC (United States); Forschungszentrum Julich GmbH, Julich (Germany)
  2. Saint Joseph's Univ., Philadelphia, PA (United States)
  3. Duke Univ., Durham, NC (United States)
Publication Date:
Research Org.:
Duke Univ., Durham, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1235120
Alternate Identifier(s):
OSTI ID: 1347987
Grant/Contract Number:  
SC0001517
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 112; Journal Issue: 45; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electron; polaron; delocalized; organic; conjugated

Citation Formats

Rawson, Jeff, Angiolillo, Paul J., and Therien, Michael J. Extreme electron polaron spatial delocalization in π-conjugated materials. United States: N. p., 2015. Web. doi:10.1073/pnas.1512318112.
Rawson, Jeff, Angiolillo, Paul J., & Therien, Michael J. Extreme electron polaron spatial delocalization in π-conjugated materials. United States. doi:10.1073/pnas.1512318112.
Rawson, Jeff, Angiolillo, Paul J., and Therien, Michael J. Wed . "Extreme electron polaron spatial delocalization in π-conjugated materials". United States. doi:10.1073/pnas.1512318112.
@article{osti_1235120,
title = {Extreme electron polaron spatial delocalization in π-conjugated materials},
author = {Rawson, Jeff and Angiolillo, Paul J. and Therien, Michael J.},
abstractNote = {The electron polaron, a spin-1/2 excitation, is the fundamental negative charge carrier in π-conjugated organic materials. Large polaron spatial dimensions result from weak electron-lattice coupling and thus identify materials with unusually low barriers for the charge transfer reactions that are central to electronic device applications. In this paper, we demonstrate electron polarons in π-conjugated multiporphyrin arrays that feature vast areal delocalization. This finding is evidenced by concurrent optical and electron spin resonance measurements, coupled with electronic structure calculations that suggest atypically small reorganization energies for one-electron reduction of these materials. Finally, because the electron polaron dimension can be linked to key performance metrics in organic photovoltaics, light-emitting diodes, and a host of other devices, these findings identify conjugated materials with exceptional optical, electronic, and spintronic properties.},
doi = {10.1073/pnas.1512318112},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 45,
volume = 112,
place = {United States},
year = {2015},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1512318112

Citation Metrics:
Cited by: 9 works
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Works referenced in this record:

Polaron spin current transport in organic semiconductors
journal, March 2014

  • Watanabe, Shun; Ando, Kazuya; Kang, Keehoon
  • Nature Physics, Vol. 10, Issue 4
  • DOI: 10.1038/nphys2901

Electron-phonon coupling for aromatic molecular crystals: Possible consequences for their superconductivity
journal, October 1998


Hole- and Electron-Vibrational Couplings in Oligoacene Crystals: Intramolecular Contributions
journal, December 2002


Imide- and Amide-Functionalized Polymer Semiconductors
journal, September 2014

  • Guo, Xugang; Facchetti, Antonio; Marks, Tobin J.
  • Chemical Reviews, Vol. 114, Issue 18
  • DOI: 10.1021/cr500225d

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

Poly(3-decylthiophene) Radical Anions and Cations in Solution: Single and Multiple Polarons and Their Delocalization Lengths in Conjugated Polymers
journal, December 2012

  • Takeda, Norihiko; Miller, John R.
  • The Journal of Physical Chemistry B, Vol. 116, Issue 50
  • DOI: 10.1021/jp3096242

Spatial Extent of Wave Functions of Gate-Induced Hole Carriers in Pentacene Field-Effect Devices as Investigated by Electron Spin Resonance
journal, December 2006


Direct observation of the charge carrier concentration in organic field-effect transistors by electron spin resonance
journal, March 2009

  • Tanaka, Hisaaki; Watanabe, Shun-ichiro; Ito, Hiroshi
  • Applied Physics Letters, Vol. 94, Issue 10
  • DOI: 10.1063/1.3100193

Highly-efficient charge separation and polaron delocalization in polymer–fullerene bulk-heterojunctions: a comparative multi-frequency EPR and DFT study
journal, January 2013

  • Niklas, Jens; Mardis, Kristy L.; Banks, Brian P.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 24
  • DOI: 10.1039/c3cp51477c

Coherent ultrafast charge transfer in an organic photovoltaic blend
journal, May 2014


The Role of Driving Energy and Delocalized States for Charge Separation in Organic Semiconductors
journal, February 2012


Ultrafast Long-Range Charge Separation in Organic Semiconductor Photovoltaic Diodes
journal, December 2013


Mesoscopic Features of Charge Generation in Organic Semiconductors
journal, July 2014

  • Savoie, Brett M.; Jackson, Nicholas E.; Chen, Lin X.
  • Accounts of Chemical Research, Vol. 47, Issue 11
  • DOI: 10.1021/ar5000852

Highly conjugated, acetylenyl bridged porphyrins: new models for light-harvesting antenna systems
journal, May 1994


Decoupling Optical and Potentiometric Band Gaps in π-Conjugated Materials
journal, July 2002

  • Susumu, Kimihiro; Therien, Michael J.
  • Journal of the American Chemical Society, Vol. 124, Issue 29
  • DOI: 10.1021/ja0203925

Exceptional Near-Infrared Fluorescence Quantum Yields and Excited-State Absorptivity of Highly Conjugated Porphyrin Arrays
journal, July 2006

  • Duncan, Timothy V.; Susumu, Kimihiro; Sinks, Louise E.
  • Journal of the American Chemical Society, Vol. 128, Issue 28
  • DOI: 10.1021/ja061897o

Conjugated Chromophore Arrays with Unusually Large Hole Polaron Delocalization Lengths
journal, July 2006

  • Susumu, Kimihiro; Frail, Paul R.; Angiolillo, Paul J.
  • Journal of the American Chemical Society, Vol. 128, Issue 26
  • DOI: 10.1021/ja0614823

Long-range electron tunnelling in oligo-porphyrin molecular wires
journal, July 2011

  • Sedghi, Gita; García-Suárez, Víctor M.; Esdaile, Louisa J.
  • Nature Nanotechnology, Vol. 6, Issue 8
  • DOI: 10.1038/nnano.2011.111

Nature of biological electron transfer
journal, February 1992

  • Moser, Christopher C.; Keske, Jonathan M.; Warncke, Kurt
  • Nature, Vol. 355, Issue 6363
  • DOI: 10.1038/355796a0

Electron Spin Resonance of Chlorophyll and the Origin of Signal I in Photosynthesis
journal, March 1971

  • Norris, J. R.; Uphaus, R. A.; Crespi, H. L.
  • Proceedings of the National Academy of Sciences, Vol. 68, Issue 3
  • DOI: 10.1073/pnas.68.3.625

Syntheses and electronic structures of decamethylmetallocenes
journal, April 1982

  • Robbins, J. L.; Edelstein, N.; Spencer, B.
  • Journal of the American Chemical Society, Vol. 104, Issue 7
  • DOI: 10.1021/ja00371a017

Electronic Structure and Dynamic Jahn‐Teller Effect of Cobaltocene from EPR and Optical Studies
journal, July 1972

  • Ammeter, J. H.; Swalen, J. D.
  • The Journal of Chemical Physics, Vol. 57, Issue 2
  • DOI: 10.1063/1.1678300

Negative Ions of Porphin Metal Complexes
journal, March 1963

  • Closs, G. L.; Closs, L. E.
  • Journal of the American Chemical Society, Vol. 85, Issue 6
  • DOI: 10.1021/ja00889a038

Characterization of reduced porphyrinatozinc(II) complexes by EPR/ENDOR/TRIPLE and optical absorption spectroscopy
journal, August 1997


Frontier orbitals of porphyrin electron donors in biomimetic model compounds - partial lifting of orbital degeneracy in asymmetric porphyrins studied by EPR on anion radicals
journal, December 1996

  • Huber, Martina; Fuhs, Michael
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 100, Issue 12
  • DOI: 10.1002/bbpc.19961001223

A graphical user-friendly interface for MCR-ALS: a new tool for multivariate curve resolution in MATLAB
journal, March 2005

  • Jaumot, Joaquim; Gargallo, Raimundo; de Juan, Anna
  • Chemometrics and Intelligent Laboratory Systems, Vol. 76, Issue 1
  • DOI: 10.1016/j.chemolab.2004.12.007

Optical absorption from polarons in a model of polyacetylene
journal, April 1983


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

Electron transfers in chemistry and biology
journal, August 1985

  • Marcus, R. A.; Sutin, Norman
  • Biochimica et Biophysica Acta (BBA) - Reviews on Bioenergetics, Vol. 811, Issue 3
  • DOI: 10.1016/0304-4173(85)90014-X

Estimation of inner shell Marcus terms for amino nitrogen compounds by molecular orbital calculations
journal, February 1987

  • Nelsen, Stephen F.; Blackstock, Silas C.; Kim, Yaesil
  • Journal of the American Chemical Society, Vol. 109, Issue 3
  • DOI: 10.1021/ja00237a007

MCR-BANDS: A user friendly MATLAB program for the evaluation of rotation ambiguities in Multivariate Curve Resolution
journal, October 2010


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

Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr
journal, May 1989


Compact contracted basis sets for third-row atoms: Ga-Kr
journal, November 1990

  • Binning, R. C.; Curtiss, L. A.
  • Journal of Computational Chemistry, Vol. 11, Issue 10
  • DOI: 10.1002/jcc.540111013

Extension of Gaussian-2 (G2) theory to molecules containing third-row atoms K and Ca
journal, October 1997

  • Blaudeau, Jean-Philippe; McGrath, Mark P.; Curtiss, Larry A.
  • The Journal of Chemical Physics, Vol. 107, Issue 13
  • DOI: 10.1063/1.474865

Extension of Gaussian‐2 theory to molecules containing third‐row atoms Ga–Kr
journal, October 1995

  • Curtiss, Larry A.; McGrath, Mark P.; Blaudeau, Jean‐Philippe
  • The Journal of Chemical Physics, Vol. 103, Issue 14
  • DOI: 10.1063/1.470438

Gaussian basis sets for molecular calculations. The representation of 3 d orbitals in transition‐metal atoms
journal, May 1977

  • Hay, P. Jeffrey
  • The Journal of Chemical Physics, Vol. 66, Issue 10
  • DOI: 10.1063/1.433731

Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980

  • Krishnan, R.; Binkley, J. S.; Seeger, R.
  • The Journal of Chemical Physics, Vol. 72, Issue 1
  • DOI: 10.1063/1.438955

Extension of Gaussian‐1 (G1) theory to bromine‐containing molecules
journal, January 1991

  • McGrath, Mark P.; Radom, Leo
  • The Journal of Chemical Physics, Vol. 94, Issue 1
  • DOI: 10.1063/1.460367

Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18
journal, May 1980

  • McLean, A. D.; Chandler, G. S.
  • The Journal of Chemical Physics, Vol. 72, Issue 10, p. 5639-5648
  • DOI: 10.1063/1.438980

Highly correlated systems. Excitation energies of first row transition metals Sc–Cu
journal, July 1989

  • Raghavachari, Krishnan; Trucks, Gary W.
  • The Journal of Chemical Physics, Vol. 91, Issue 2
  • DOI: 10.1063/1.457230

Gaussian Basis Set for Molecular Wavefunctions Containing Third‐Row Atoms
journal, February 1970

  • Wachters, A. J. H.
  • The Journal of Chemical Physics, Vol. 52, Issue 3
  • DOI: 10.1063/1.1673095

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    A naphthalene-fused dimer of an anti-aromatic expanded isophlorin
    journal, January 2017

    • Reddy, Baddigam Kiran; Rawson, Jeff; Gadekar, Santosh C.
    • Chemical Communications, Vol. 53, Issue 58
    • DOI: 10.1039/c7cc04050d