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Title: Electronic Tuning of Mixed Quinoidal-Aromatic Conjugated Polyelectrolytes: Direct Ionic Substitution on Polymer Main-Chains

Abstract

Abstract The synthesis of conjugated polymers with ionic substituents directly bound to their main chain repeat units is a strategy for generating strongly electron‐accepting conjugated polyelectrolytes, as demonstrated through the synthesis of a series of ionic azaquinodimethane (iAQM) compounds. The introduction of cationic substituents onto the quinoidal para ‐azaquinodimethane (AQM) core gives rise to a strongly electron‐accepting building block, which can be employed in the synthesis of ionic small molecules and conjugated polyelectrolytes (CPEs). Electrochemical measurements alongside theoretical calculations indicate notably low‐lying LUMO values for the iAQMs. The optical band gaps measured for these compounds are highly tunable based on structure, ranging from 2.30 eV in small molecules down to 1.22 eV in polymers. The iAQM small molecules and CPEs showcase the band gap reduction effects of combining the donor‐acceptor strategy with the bond‐length alternation reduction strategy. As a demonstration of their utility, the iAQM CPEs so generated were used as active agents in photothermal therapy.

Authors:
ORCiD logo [1];  [2];  [3];  [3];  [2]; ORCiD logo [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  2. Chinese Academy of Sciences, Beijing (China)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1581610
Alternate Identifier(s):
OSTI ID: 1576804
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 50; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Anderson, Christopher L., Dai, Nan, Teat, Simon J., He, Bo, Wang, Shu, and Liu, Yi. Electronic Tuning of Mixed Quinoidal-Aromatic Conjugated Polyelectrolytes: Direct Ionic Substitution on Polymer Main-Chains. United States: N. p., 2019. Web. doi:10.1002/anie.201908609.
Anderson, Christopher L., Dai, Nan, Teat, Simon J., He, Bo, Wang, Shu, & Liu, Yi. Electronic Tuning of Mixed Quinoidal-Aromatic Conjugated Polyelectrolytes: Direct Ionic Substitution on Polymer Main-Chains. United States. https://doi.org/10.1002/anie.201908609
Anderson, Christopher L., Dai, Nan, Teat, Simon J., He, Bo, Wang, Shu, and Liu, Yi. Mon . "Electronic Tuning of Mixed Quinoidal-Aromatic Conjugated Polyelectrolytes: Direct Ionic Substitution on Polymer Main-Chains". United States. https://doi.org/10.1002/anie.201908609. https://www.osti.gov/servlets/purl/1581610.
@article{osti_1581610,
title = {Electronic Tuning of Mixed Quinoidal-Aromatic Conjugated Polyelectrolytes: Direct Ionic Substitution on Polymer Main-Chains},
author = {Anderson, Christopher L. and Dai, Nan and Teat, Simon J. and He, Bo and Wang, Shu and Liu, Yi},
abstractNote = {Abstract The synthesis of conjugated polymers with ionic substituents directly bound to their main chain repeat units is a strategy for generating strongly electron‐accepting conjugated polyelectrolytes, as demonstrated through the synthesis of a series of ionic azaquinodimethane (iAQM) compounds. The introduction of cationic substituents onto the quinoidal para ‐azaquinodimethane (AQM) core gives rise to a strongly electron‐accepting building block, which can be employed in the synthesis of ionic small molecules and conjugated polyelectrolytes (CPEs). Electrochemical measurements alongside theoretical calculations indicate notably low‐lying LUMO values for the iAQMs. The optical band gaps measured for these compounds are highly tunable based on structure, ranging from 2.30 eV in small molecules down to 1.22 eV in polymers. The iAQM small molecules and CPEs showcase the band gap reduction effects of combining the donor‐acceptor strategy with the bond‐length alternation reduction strategy. As a demonstration of their utility, the iAQM CPEs so generated were used as active agents in photothermal therapy.},
doi = {10.1002/anie.201908609},
journal = {Angewandte Chemie (International Edition)},
number = 50,
volume = 58,
place = {United States},
year = {Mon Oct 07 00:00:00 EDT 2019},
month = {Mon Oct 07 00:00:00 EDT 2019}
}

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Cited by: 24 works
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Figures / Tables:

Scheme 1 Scheme 1: (a) Illustration of two different types of CPEs; (b) structural diagram of the dicationic iAQM as a building block for CPEs (Nu: neutral nucleophiles such as pyridine, triphenylphosphine, etc.)

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