Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling

Thin films of poly(arylene ethynylene)-conjugated polymers, including low-energy-gap donor–acceptor polymers, can be prepared via stepwise polymerization utilizing surface-confined Sonogashira cross-coupling. This robust and efficient polymerization protocol yields conjugated polymers with a precise...

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Main Authors: Sang Gil Youm, Mitchell T. Howell, Chien-Hung Chiang, Lu Lu, Neepa M. K. Kuruppu Arachchige, John F. Ankner, Joseph Strzalka, Yaroslav Losovyj, Jayne C. Garno, Evgueni E. Nesterov
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Language:English
Published: MDPI AG 2024-11-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/29/22/5466
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author Sang Gil Youm
Mitchell T. Howell
Chien-Hung Chiang
Lu Lu
Neepa M. K. Kuruppu Arachchige
John F. Ankner
Joseph Strzalka
Yaroslav Losovyj
Jayne C. Garno
Evgueni E. Nesterov
author_facet Sang Gil Youm
Mitchell T. Howell
Chien-Hung Chiang
Lu Lu
Neepa M. K. Kuruppu Arachchige
John F. Ankner
Joseph Strzalka
Yaroslav Losovyj
Jayne C. Garno
Evgueni E. Nesterov
author_sort Sang Gil Youm
collection DOAJ
description Thin films of poly(arylene ethynylene)-conjugated polymers, including low-energy-gap donor–acceptor polymers, can be prepared via stepwise polymerization utilizing surface-confined Sonogashira cross-coupling. This robust and efficient polymerization protocol yields conjugated polymers with a precise molecular structure and with nanometer-level control of the organization and the uniform alignment of the macromolecular chains in the densely packed film. In addition to high stability and predictable and well-defined molecular organization and morphology, the surface-confined conjugated polymer chains experience significant interchain electronic interactions, resulting in dominating intermolecular π-electron delocalization which is primarily responsible for the electronic and spectroscopic properties of polymer films. The fluorescent films demonstrate remarkable performance in chemosensing applications, showing a turn-off fluorescent response on the sub-ppt (part per trillion) level of nitroaromatic explosives in water. This unique sensitivity is likely related to the enhanced exciton mobility in the uniformly aligned and structurally monodisperse polymer films.
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spelling doaj-art-066be2fee9014deaa9dd7cf2da68fe8b2025-08-20T02:04:59ZengMDPI AGMolecules1420-30492024-11-012922546610.3390/molecules29225466Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-CouplingSang Gil Youm0Mitchell T. Howell1Chien-Hung Chiang2Lu Lu3Neepa M. K. Kuruppu Arachchige4John F. Ankner5Joseph Strzalka6Yaroslav Losovyj7Jayne C. Garno8Evgueni E. Nesterov9Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USADepartment of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USADepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USADepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USADepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USASpallation Neutron Source, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USAX-Ray Science Division, Argonne National Laboratory, Argonne, IL 60439, USADepartment of Chemistry, Indiana University, Bloomington, IN 47401, USADepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USADepartment of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USAThin films of poly(arylene ethynylene)-conjugated polymers, including low-energy-gap donor–acceptor polymers, can be prepared via stepwise polymerization utilizing surface-confined Sonogashira cross-coupling. This robust and efficient polymerization protocol yields conjugated polymers with a precise molecular structure and with nanometer-level control of the organization and the uniform alignment of the macromolecular chains in the densely packed film. In addition to high stability and predictable and well-defined molecular organization and morphology, the surface-confined conjugated polymer chains experience significant interchain electronic interactions, resulting in dominating intermolecular π-electron delocalization which is primarily responsible for the electronic and spectroscopic properties of polymer films. The fluorescent films demonstrate remarkable performance in chemosensing applications, showing a turn-off fluorescent response on the sub-ppt (part per trillion) level of nitroaromatic explosives in water. This unique sensitivity is likely related to the enhanced exciton mobility in the uniformly aligned and structurally monodisperse polymer films.https://www.mdpi.com/1420-3049/29/22/5466Sonogashira cross-couplingstepwise polymerizationpolymer thin filmsfluorescent sensorexcitation energy transferdetection of nitroaromatic compounds
spellingShingle Sang Gil Youm
Mitchell T. Howell
Chien-Hung Chiang
Lu Lu
Neepa M. K. Kuruppu Arachchige
John F. Ankner
Joseph Strzalka
Yaroslav Losovyj
Jayne C. Garno
Evgueni E. Nesterov
Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling
Molecules
Sonogashira cross-coupling
stepwise polymerization
polymer thin films
fluorescent sensor
excitation energy transfer
detection of nitroaromatic compounds
title Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling
title_full Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling
title_fullStr Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling
title_full_unstemmed Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling
title_short Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling
title_sort precision synthesis of conjugated polymer films by surface confined stepwise sonogashira cross coupling
topic Sonogashira cross-coupling
stepwise polymerization
polymer thin films
fluorescent sensor
excitation energy transfer
detection of nitroaromatic compounds
url https://www.mdpi.com/1420-3049/29/22/5466
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