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

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

doi:10.3390/molecules29225466

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

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

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	English
Article number	5466
Journal	Molecules
Volume	29
Issue number	22
DOIs	https://doi.org/10.3390/molecules29225466
State	Published - Nov 2024
Externally published	Yes

Funding

Kind appreciation is due to Xin Li for the help with analyzing the GISAXS data. This research used the resources at Spallation Neutron Source, the DOE Office of the Science User Facility operated by Oak Ridge National Laboratory, and the resources of the Advanced Photon Source, the DOE Office of the Science User Facility operated by the Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This research was supported by the U.S. National Science Foundation (NSF) under the grant CHE-2004117. The purchase of the NMR spectrometer used to obtain the results included in this publication was supported by the NSF under the MRI award CHE-2117776.

Keywords

detection of nitroaromatic compounds
excitation energy transfer
fluorescent sensor
polymer thin films
Sonogashira cross-coupling
stepwise polymerization

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10.3390/molecules29225466

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title = "Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling",

abstract = "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.",

keywords = "detection of nitroaromatic compounds, excitation energy transfer, fluorescent sensor, polymer thin films, Sonogashira cross-coupling, stepwise polymerization",

author = "Youm, \{Sang Gil\} and Howell, \{Mitchell T.\} and Chiang, \{Chien Hung\} and Lu Lu and \{Kuruppu Arachchige\}, \{Neepa M.K.\} and Ankner, \{John F.\} and Joseph Strzalka and Yaroslav Losovyj and Garno, \{Jayne C.\} and Nesterov, \{Evgueni E.\}",

note = "Publisher Copyright: {\textcopyright} 2024 by the authors.",

year = "2024",

month = nov,

doi = "10.3390/molecules29225466",

language = "English",

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journal = "Molecules",

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T1 - Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling

AU - Youm, Sang Gil

AU - Howell, Mitchell T.

AU - Chiang, Chien Hung

AU - Lu, Lu

AU - Kuruppu Arachchige, Neepa M.K.

AU - Ankner, John F.

AU - Strzalka, Joseph

AU - Losovyj, Yaroslav

AU - Garno, Jayne C.

AU - Nesterov, Evgueni E.

PY - 2024/11

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N2 - 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.

AB - 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.

KW - detection of nitroaromatic compounds

KW - excitation energy transfer

KW - fluorescent sensor

KW - polymer thin films

KW - Sonogashira cross-coupling

KW - stepwise polymerization

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DO - 10.3390/molecules29225466

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ER -

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

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