Atomic-Level Insight into the Postsynthesis Band Gap Engineering of a Lewis Base Polymer Using Lewis Acid Tris(pentafluorophenyl)borane - Université de Lille Accéder directement au contenu
Article Dans Une Revue Chemistry of Materials Année : 2019

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

Brett Yurash
  • Fonction : Auteur
Dirk Leifert
  • Fonction : Auteur
David Xi Cao
  • Fonction : Auteur
Simon Biberger
  • Fonction : Auteur
Viktor V. Brus
  • Fonction : Auteur
Martin Seifrid
  • Fonction : Auteur
Peter J. Santiago
  • Fonction : Auteur
Anna Köhler
  • Fonction : Auteur
Bradley F. Chmelka
  • Fonction : Auteur
Guillermo C. Bazan
  • Fonction : Auteur
Thuc-Quyen Nguyen
  • Fonction : Auteur

Résumé

In this report, 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.
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Dates et versions

hal-04532696 , version 1 (04-04-2024)

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Brett Yurash, Dirk Leifert, Manjunatha Reddy, David Xi Cao, Simon Biberger, et al.. Atomic-Level Insight into the Postsynthesis Band Gap Engineering of a Lewis Base Polymer Using Lewis Acid Tris(pentafluorophenyl)borane. Chemistry of Materials, 2019, Chemistry of Materials, 31 (17), pp.6715-6725. ⟨10.1021/acs.chemmater.9b01224⟩. ⟨hal-04532696⟩
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