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

Journal Article · · Angewandte Chemie
ORCiD logo [1];  [2];  [3];  [4];  [2]; ORCiD logo [4]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  2. Chinese Academy of Sciences (CAS), Beijing (China)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

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. Finally, as a demonstration of their utility, the iAQM CPEs so generated were used as active agents in photothermal therapy.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division (SC-22.3); USDOE
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1599824
Alternate ID(s):
OSTI ID: 1572118
Journal Information:
Angewandte Chemie, Vol. 131, Issue 50; ISSN 0044-8249
Publisher:
German Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (100)

Rigid-rod polyelectrolytes: synthesis of sulfonated poly(p-phenylene)s journal September 1994
Low-Bandgap Near-IR Conjugated Polymers/Molecules for Organic Electronics journal August 2015
Conjugated polyelectrolyte and zinc oxide stacked structure as an interlayer in highly efficient and stable organic photovoltaic cells journal January 2013
A Porphyrin-Based Conjugated Polymer for Highly Efficient In Vitro and In Vivo Photothermal Therapy journal September 2016
Conjugated Polyelectrolytes: Synthesis, Photophysics, and Applications journal June 2009
Quinoidal/Aromatic Transformations in π-Conjugated Oligomers: Vibrational Raman studies on the Limits of Rupture for π-Bonds journal February 2017
A Novel Approach Toward Low Optical Band Gap Polysquaraines journal August 2001
Low-bandgap conjugated polymers. A joint experimental and theoretical study of the structure of polyisothianaphthene journal December 1992
Neuromorphic Functions in PEDOT:PSS Organic Electrochemical Transistors journal October 2015
Characterization of Association Colloids of Amphiphilic Poly( p -phenylene)sulfonates in Aqueous Solution journal August 2001
Theoretical design of polymeric conductors journal January 1987
Electrochemical Logic Circuits journal February 2005
Fluorescent Conjugated Polyelectrolytes for Bioimaging journal August 2011
Graphene-Based Photothermal Agent for Rapid and Effective Killing of Bacteria journal January 2013
Facile Doping of Anionic Narrow-Band-Gap Conjugated Polyelectrolytes During Dialysis journal November 2013
Efficient blue light emitting devices based on rigid-rod polyelectrolytes journal July 1996
In vivo near-infrared fluorescence imaging journal October 2003
A non-volatile organic electrochemical device as a low-voltage artificial synapse for neuromorphic computing journal February 2017
Cyclophane chemistry: bent and battered benzene rings journal June 1971
Vapor Deposition Polymerization of para-Xylylene Derivatives-Mechanism and Applications journal January 2007
Some remarks on the CH2[graphic omitted]CH2 molecule journal January 1947
“End-Only” Functionalized Oligo(phenylene ethynylene)s: Synthesis, Photophysical and Biocidal Activity journal October 2010
Multifunctional Cationic Poly(p-phenylene vinylene) Polyelectrolytes for Selective Recognition, Imaging, and Killing of Bacteria Over Mammalian Cells journal September 2011
A–D–A small molecules for solution-processed organic photovoltaic cells journal January 2015
Relationship between band gap and bond length alternation in organic conjugated polymers journal April 1985
High-Performance Polymer Solar Cells with Electrostatic Layer-by-Layer Self-Assembled Conjugated Polyelectrolytes as the Cathode Interlayer journal May 2015
Near-Infrared Light-Emitting Ambipolar Organic Field-Effect Transistors journal March 2007
Levels of Structure Formation in Aqueous Solutions of Anisotropic Association Colloids Consisting of Rodlike Polyelectrolytes journal August 2001
Design of Narrow-Bandgap Polymers. Syntheses and Properties of Monomers and Polymers Containing Aromatic-Donor and o -Quinoid-Acceptor Units journal January 1996
Nanostructured Dihexadecyldimethylammonium-Poly(1,4-phenylene-ethinylene-carboxylate): An Ionic Complex with Blue Electroluminescence journal February 1999
Conductive Conjugated Polyelectrolyte as Hole-Transporting Layer for Organic Bulk Heterojunction Solar Cells journal October 2013
Donor–acceptor type low band gap polymers: polysquaraines and related systems journal January 2003
Narrow Band Gap Conjugated Polyelectrolytes journal December 2017
Nanomaterials formulations for photothermal and photodynamic therapy of cancer journal June 2013
Conjugated Polymers in Bioelectronics journal May 2018
Conjugated-Polymer-Amplified Sensing, Imaging, and Therapy journal June 2017
[2.2]Paracyclophane in Polymerchemie und Materialwissenschaften journal December 2008
Squaraine Dye Based Molecular Wires Containing Flexible Oxyethylene Chains as Sensors. Enhanced Fluorescence Response on Li + Recognition journal September 1999
Poly( p -xylylene) and Its Derivatives by Chemical Vapor Deposition:  Synthesis, Mechanism, and Structure journal December 1998
Which fluorophore is brightest? A comparison of the staining obtained using fluorescein, tetramethylrhodamine, lissamine rhodamine, texas red, and cyanine 3.18 journal September 1992
Organic Heptamethine Salts for Photovoltaics and Detectors with Near-Infrared Photoresponse up to 1600 nm journal April 2016
The Rise of Organic Bioelectronics journal September 2013
In aqua synthesis of water-soluble poly(p-phenylene) derivatives journal September 1991
Syntheses and Properties of π -Conjugated Polymers Containing Chromophore. 1. Water-Soluble Small-Bandgap Polymer Backbone journal June 1997
Thieno[3,4- b ]pyrazine-based oligothiophenes: simple models of donor–acceptor polymeric materials journal January 2014
[2.2]Paracyclophanes in Polymer Chemistry and Materials Science journal December 2008
Visual optical discrimination and detection of microbial pathogens based on diverse interactions of conjugated polyelectrolytes with cells journal January 2011
[2.2](2,5)Pyrazinophanes: Synthesis and Molecular Structure journal January 1988
Synthesis of novel triphenylamine-based conjugated polyelectrolytes and their application as hole-transport layers in polymeric light-emitting diodes journal January 2006
A new class of small band gap organic polymer conductors journal August 1992
Light-Induced Biocidal Action of Conjugated Polyelectrolytes Supported on Colloids journal August 2008
para -Azaquinodimethane: A Compact Quinodimethane Variant as an Ambient Stable Building Block for High-Performance Low Band Gap Polymers journal June 2017
Narrow band gap conjugated polyelectrolytes for photothermal killing of bacteria journal January 2015
Konjugierte Polyelektrolyte: Synthese, Photophysik und Anwendungen journal June 2009
Conjugated polyelectrolytes: A new class of semiconducting material for organic electronic devices journal August 2013
NIR dyes for bioimaging applications journal February 2010
Neihumicin, a new cytotoxic antibiotic from Micromonospora neihuensis. II. Structural determination and total synthesis. journal January 1988
Condensation of 1,4-diacetylpiperazine-2,5-dione with aldehydes journal January 1974
Electroluminescent Polyelectrolyte−Surfactant Complexes journal August 2001
Biocidal Activity of a Light-Absorbing Fluorescent Conjugated Polyelectrolyte journal October 2005
Conjugated polymer microparticles for selective cancer cell image-guided photothermal therapy journal January 2015
Chinoide/Aromatische Umwandlungen in π-konjugierten Oligomeren: Raman-Schwingungsspektroskopie an der Grenze zum π-Bindungsbruch journal February 2017
Cationic Conjugated Polymers for Discrimination of Microbial Pathogens journal April 2014
Synthesis and Properties of Two Cationic Narrow Band Gap Conjugated Polyelectrolytes journal March 2013
Morphological Characterization of the Molecular Superstructure of Polyphenylene Ethynylene Derivatives journal April 1999
Syntheses of Conjugated Polymers for Photonics journal September 2010
Conjugated polymer and drug co-encapsulated nanoparticles for Chemo- and Photo-thermal Combination Therapy with two-photon regulated fast drug release journal January 2015
Organic thin-film transistors journal April 2010
Cyclodextrin-Threaded Conjugated Polyrotaxanes for Organic Electronics: The Influence of the Counter Cations journal August 2008
Neihumicin, a new cytotoxic antibiotic from Micromonospora neihuensis. III. Structure-activity relationships. journal January 1988
Ultrathin interlayers of a conjugated polyelectrolyte for low work-function cathodes in efficient inverted organic solar cells journal March 2013
Radical ions of [2.2](2,5)pyrazinophanes: an electron paramagnetic resonance study journal January 1992
Conjugated Polyelectrolyte Blends for Electrochromic and Electrochemical Transistor Devices journal August 2015
The organic electrochemical transistor for biological applications journal January 2015
Investigation of a Conjugated Polyelectrolyte Interlayer for Inverted Polymer:Fullerene Solar Cells journal March 2013
Organic electrochemical transistors journal January 2018
Non-fullerene acceptors for organic photovoltaics: an emerging horizon journal January 2014
[2.2](2,6)- and [2.2](2,5)Pyrazinophanes: Synthesis and Molecular Structure journal March 1990
Facile Doping of Anionic Narrow-Band-Gap Conjugated Polyelectrolytes During Dialysis journal November 2013
Conjugated polyelectrolytes as fluorescent sensors journal December 2009
Alternate donor-acceptor small-band-gap semiconducting polymers; Polysquaraines and polycroconaines journal March 1993
The Chemistry of Xylylenes. III. Some Reactions of p-Xylylene that Occur by Free Radical Intermediates 2 journal January 1960
Insight into the Mechanism of Antimicrobial Conjugated Polyelectrolytes: Lipid Headgroup Charge and Membrane Fluidity Effects journal April 2010
Polymerizations of nitrogen-containing heterophanes by vapor deposition method, transformation to polymeric films bearing a conjugated structure, and their properties journal September 1995
Electronic structure and optical absorption of poly(biisothianaphthene-methine) and poly(isonaphthothiophene-thiophene): two low-band-gap polymers journal December 1991
Functionalized Conjugated Polyelectrolytes for Biological Sensing and Imaging journal May 2016
Biocompatible Conjugated Polymer Nanoparticles for Efficient Photothermal Tumor Therapy journal November 2014
The rise of plastic bioelectronics journal December 2016
Organic salt photovoltaics journal January 2017
Vibrational Raman Shifts and Aromaticity: The Case of Oligothiophenes journal July 2015
Water-Soluble Conjugated Polymers for Imaging, Diagnosis, and Therapy journal May 2012
Organic non-fullerene acceptors for organic photovoltaics journal January 2011
The synthesis and targeting of PPP-type copolymers to breast cancer cells: Multifunctional platforms for imaging and diagnosis journal January 2012
Discovery of a Class of Diketopiperazines as Antiprion Compounds journal June 2010
Conjugated ionic polyacetylenes. 3. Polymerization of ethynylpyridinium salts journal May 1991
Improved High-Efficiency Organic Solar Cells via Incorporation of a Conjugated Polyelectrolyte Interlayer journal June 2011
Cyclodextrin-Threaded Conjugated Polyrotaxanes for Organic Electronics: The Influence of the Counter Cations journal December 2009
Donor—Acceptor Type Low Band Gap Polymers: Polysquaraines and Related Systems journal September 2003
Conjugated Polymers in Bioelectronics. journalarticle January 2018
Organic Electrochemical Transistors text January 2018

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