TY - JOUR
T1 - Vibrational Spectroscopy Reveals Effects of Electron Push-Pull and Solvent Polarity on Electron Delocalization in Radical Anions of Donor-Acceptor Compounds
AU - Boudreau, Andrew M.
AU - Wilson, Reid W.
AU - Yang, Mengshijie
AU - Grills, David C.
AU - Mani, Tomoyasu
N1 - Funding Information:
T.M. is grateful for startup funds from the University of Connecticut. Part of this work and use of the LEAF facility of the BNL Accelerator Center for Energy Research and the computer Cluster at the Center for Functional Nanomaterials were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences, under contract no. DE-SC0012704, and part was supported by BNL Laboratory Directed Research and Development (LDRD) (project numbers 18-056 and 19-015).
Funding Information:
T.M. is grateful for startup funds from the University of Connecticut. Part of this work and use of the LEAF facility of the BNL Accelerator Center for Energy Research and the computer Cluster at the Center for Functional Nanomaterials were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences Division of Chemical Sciences, Geosciences & Biosciences, under contract no. DE-SC0012704, and part was supported by BNL Laboratory Directed Research and Development (LDRD) (project numbers 18-056 and 19-015).
Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/2/27
Y1 - 2020/2/27
N2 - The nature of excess electrons has been studied in donor-acceptor (D-A) compounds based on substituted triarylamines and a nitrile-functionalized fluorene by changing the substituents on the triarylamines and also the solvent polarity. We observed that both electron push-pull capability at the distant location in the amine donor unit and solvation in solvents of varying polarity significantly affect the nitrile ν(CN) vibrations of the fluorene acceptor unit in radical anions of these D-A compounds. Quantum calculations show that the push-pull capability translates the position of an excess electron while keeping its width relatively constant. On the other hand, solvation changes both, making an electron more compact in polar media. The current study points to the idea that solvation plays a more significant role in controlling the nature of excess electrons, while synthetic modification that influences electron push-pull capability enables further tuning.
AB - The nature of excess electrons has been studied in donor-acceptor (D-A) compounds based on substituted triarylamines and a nitrile-functionalized fluorene by changing the substituents on the triarylamines and also the solvent polarity. We observed that both electron push-pull capability at the distant location in the amine donor unit and solvation in solvents of varying polarity significantly affect the nitrile ν(CN) vibrations of the fluorene acceptor unit in radical anions of these D-A compounds. Quantum calculations show that the push-pull capability translates the position of an excess electron while keeping its width relatively constant. On the other hand, solvation changes both, making an electron more compact in polar media. The current study points to the idea that solvation plays a more significant role in controlling the nature of excess electrons, while synthetic modification that influences electron push-pull capability enables further tuning.
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U2 - 10.1021/acs.jpcb.9b11747
DO - 10.1021/acs.jpcb.9b11747
M3 - Article
C2 - 32011147
AN - SCOPUS:85081168349
VL - 124
SP - 1543
EP - 1549
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
SN - 1520-6106
IS - 8
ER -