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Title: Atomic-Level Insight into the Postsynthesis Band Gap Engineering of a Lewis Base Polymer Using Lewis Acid Tris(pentafluorophenyl)borane

Abstract

Here, we investigate the binding properties of the Lewis acid tris(pentafluorophenyl)borane with a Lewis base semiconducting polymer, PFPT, and the subsequent mechanism of band gap reduction. Experiments and quantum chemical calculations confirm that the formation of a Lewis acid adduct is energetically favorable (ΔG° < -0.2 eV), with preferential binding at the pyridyl nitrogen in the polymer backbone over other Lewis base sites. Upon adduct formation, ultraviolet photoelectron spectroscopy indicates only a slight decrease in the HOMO energy, implying that a larger reduction in the LUMO energy is primarily responsible for the observed optical band gap narrowing (ΔEopt = 0.3 eV). Herein, we also provide the first spatially resolved picture of how Lewis acid adducts form in heterogeneous, disordered polymer/tris(pentafluorophenyl)borane thin films via one- (1D) and two-dimensional (2D) solid-state nuclear magnetic resonance. Notably, solid-state 1D 11B, 13C{1H}, and 13C{19F} cross-polarization magic-angle spinning (CP-MAS) NMR and 2D 1H{19F} and 1H{1H} correlation NMR analyses establish that BCF molecules are intercalated between branched C16H33 side chains with the boron atom facing toward the pyridyl nitrogen atoms of PFPT.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1];  [1];  [1]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, Santa Barbara, CA (United States)
  2. Univ. of California, Santa Barbara, CA (United States); Univ. of Bayreuth (Germany)
  3. Univ. of Bayreuth (Germany)
Publication Date:
Research Org.:
Univ. of California, Santa Barbara, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Alexander von Humboldt Foundation; Bavaria California Technology Centre (BaCaTec); National Science Foundation (NSF); Mitsubishi Chemical-Centre for Advanced Materials
OSTI Identifier:
1593943
Alternate Identifier(s):
OSTI ID: 1661629
Grant/Contract Number:  
SC0017659; AC02-05CH11231; 1650114; DMR-1720256
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 17; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Adducts; Lewis acids; Nitrogen; Nuclear magnetic resonance spectroscopy; Polymers

Citation Formats

Yurash, Brett, Leifert, Dirk, Reddy, G. N. Manjunatha, Cao, David Xi, Biberger, Simon, Brus, Viktor V., Seifrid, Martin, Santiago, Peter J., Köhler, Anna, Chmelka, Bradley F., Bazan, Guillermo C., and Nguyen, Thuc-Quyen. Atomic-Level Insight into the Postsynthesis Band Gap Engineering of a Lewis Base Polymer Using Lewis Acid Tris(pentafluorophenyl)borane. United States: N. p., 2019. Web. doi:10.1021/acs.chemmater.9b01224.
Yurash, Brett, Leifert, Dirk, Reddy, G. N. Manjunatha, Cao, David Xi, Biberger, Simon, Brus, Viktor V., Seifrid, Martin, Santiago, Peter J., Köhler, Anna, Chmelka, Bradley F., Bazan, Guillermo C., & Nguyen, Thuc-Quyen. Atomic-Level Insight into the Postsynthesis Band Gap Engineering of a Lewis Base Polymer Using Lewis Acid Tris(pentafluorophenyl)borane. United States. https://doi.org/10.1021/acs.chemmater.9b01224
Yurash, Brett, Leifert, Dirk, Reddy, G. N. Manjunatha, Cao, David Xi, Biberger, Simon, Brus, Viktor V., Seifrid, Martin, Santiago, Peter J., Köhler, Anna, Chmelka, Bradley F., Bazan, Guillermo C., and Nguyen, Thuc-Quyen. Wed . "Atomic-Level Insight into the Postsynthesis Band Gap Engineering of a Lewis Base Polymer Using Lewis Acid Tris(pentafluorophenyl)borane". United States. https://doi.org/10.1021/acs.chemmater.9b01224. https://www.osti.gov/servlets/purl/1593943.
@article{osti_1593943,
title = {Atomic-Level Insight into the Postsynthesis Band Gap Engineering of a Lewis Base Polymer Using Lewis Acid Tris(pentafluorophenyl)borane},
author = {Yurash, Brett and Leifert, Dirk and Reddy, G. N. Manjunatha and Cao, David Xi and Biberger, Simon and Brus, Viktor V. and Seifrid, Martin and Santiago, Peter J. and Köhler, Anna and Chmelka, Bradley F. and Bazan, Guillermo C. and Nguyen, Thuc-Quyen},
abstractNote = {Here, we investigate the binding properties of the Lewis acid tris(pentafluorophenyl)borane with a Lewis base semiconducting polymer, PFPT, and the subsequent mechanism of band gap reduction. Experiments and quantum chemical calculations confirm that the formation of a Lewis acid adduct is energetically favorable (ΔG° < -0.2 eV), with preferential binding at the pyridyl nitrogen in the polymer backbone over other Lewis base sites. Upon adduct formation, ultraviolet photoelectron spectroscopy indicates only a slight decrease in the HOMO energy, implying that a larger reduction in the LUMO energy is primarily responsible for the observed optical band gap narrowing (ΔEopt = 0.3 eV). Herein, we also provide the first spatially resolved picture of how Lewis acid adducts form in heterogeneous, disordered polymer/tris(pentafluorophenyl)borane thin films via one- (1D) and two-dimensional (2D) solid-state nuclear magnetic resonance. Notably, solid-state 1D 11B, 13C{1H}, and 13C{19F} cross-polarization magic-angle spinning (CP-MAS) NMR and 2D 1H{19F} and 1H{1H} correlation NMR analyses establish that BCF molecules are intercalated between branched C16H33 side chains with the boron atom facing toward the pyridyl nitrogen atoms of PFPT.},
doi = {10.1021/acs.chemmater.9b01224},
journal = {Chemistry of Materials},
number = 17,
volume = 31,
place = {United States},
year = {Wed May 15 00:00:00 EDT 2019},
month = {Wed May 15 00:00:00 EDT 2019}
}

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