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

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

doi:10.1021/acs.chemmater.9b01224

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

Journal Article · Wed May 15 00:00:00 EDT 2019 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.9b01224· OSTI ID:1593943

^[1]; Leifert, Dirk ^[1];

^[1];

^[1]; Biberger, Simon ^[2];

^[1]; Seifrid, Martin ^[1]; Santiago, Peter J. ^[1];

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Univ. of California, Santa Barbara, CA (United States)
Univ. of California, Santa Barbara, CA (United States); Univ. of Bayreuth (Germany)
Univ. of Bayreuth (Germany)

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 (ΔE_opt = 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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Research Organization:: Univ. of California, Santa Barbara, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Sponsoring Organization:: 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

Grant/Contract Number:: SC0017659; AC02-05CH11231; 1650114; DMR-1720256

OSTI ID:: 1593943

Alternate ID(s):: OSTI ID: 1661629

Journal Information:: Chemistry of Materials, Vol. 31, Issue 17; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 32 works

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