TY - JOUR
T1 - Electron-transporting foldable alternating copolymers of perylenediimide and flexible macromolecular chains
AU - Sakurai, Tsuneaki
AU - Orito, Naomi
AU - Nagano, Shusaku
AU - Kato, Kenichi
AU - Takata, Masaki
AU - Seki, Shu
N1 - Funding Information:
This work was partially supported by the Grant-in-Aid for Scientific Research (No. 26102011, 15K21721, 26249145, and
Funding Information:
17H04880) from Japan Society for the Promotion of Science (JSPS) and research grants from the Ogasawara Foundation for the Promotion of Science & Engineering, Tateisi Science and Technology Foundation, the Eno Science Foundation, and Iketani Science and Technology Foundation. The synchrotron radiation experiments were performed at BL44B2 in SPring-8 with the approval of RIKEN (Proposal No. 20160014). GI-XS experiments were conducted in Nagoya University, supported by Nanotechnology Platform Program of MEXT, Japan (Proposal No. S-16-NU-0017). We also acknowledge Prof. Akihiro Ito for the evaluation of absolute photoluminescence quantum yield and DLS measurements for Prof. Kenji Matsuda and Prof. Takashi Hirose in Kyoto University.
Publisher Copyright:
This journal is © The Royal Society of Chemistry and the Chinese Chemical Society 2018
PY - 2018
Y1 - 2018
N2 - Tuning the electrical conductivity of conjugated macromolecules by nanostructure ordering plays a key role in developing carrier transporting materials applicable to flexible organic electronic devices. Alternating copolymers of perylene-3,4,9,10-tetracarboxylic acid diimide (PDI) and flexible macromonomers, poly(dimethylsiloxane) (PDMS), poly(ethylene glycol) (PEG), or poly(propylene glycol) (PPG), were synthesized via simple polycondensation reactions between 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and bis-amine-terminated corresponding macromonomers. Dynamic traces of absorption and fluorescence spectra of the series of alternating copolymers, with the indication of PDI chromophores, suggested the more foldable nature in tetrahydrofuran of the PDMS-based polymer than of the PEG- and PPG-based polymers. The folding capability of these polymers in solution was confirmed by fluorescence spectra and the absolute fluorescence quantum efficiency values. In the solid films, the condensed state of the polymers showed X-ray diffraction patterns of periodic structures, which depend on the type of macromolecular chains: PEG showed a highly crystallized state in contrast to the slightly crystalline PDI molecules in the PDMS and PPG-based polymers. Photoconductivity upon ultraviolet excitation has been screened by noncontact microwave measurements, and the mobility of electrons has also been characterized based on the kinetic traces of radical anions on the PDI chromophores. The negligible optical absorption observed from the PDMS-based polymers revealed the lowest photocarrier generation yield among the prepared polymers. The observed low conductivity for the PDMS-based, most foldable polymers possibly results from a lower photo-charge generation yield and thermal fluctuations of the flexible PDMS chains. The PEG-based polymer marked the largest electron mobility of 0.2 cm 2 V 1 s 1 , reflecting the highly crystalline nature of the PEG chains.
AB - Tuning the electrical conductivity of conjugated macromolecules by nanostructure ordering plays a key role in developing carrier transporting materials applicable to flexible organic electronic devices. Alternating copolymers of perylene-3,4,9,10-tetracarboxylic acid diimide (PDI) and flexible macromonomers, poly(dimethylsiloxane) (PDMS), poly(ethylene glycol) (PEG), or poly(propylene glycol) (PPG), were synthesized via simple polycondensation reactions between 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and bis-amine-terminated corresponding macromonomers. Dynamic traces of absorption and fluorescence spectra of the series of alternating copolymers, with the indication of PDI chromophores, suggested the more foldable nature in tetrahydrofuran of the PDMS-based polymer than of the PEG- and PPG-based polymers. The folding capability of these polymers in solution was confirmed by fluorescence spectra and the absolute fluorescence quantum efficiency values. In the solid films, the condensed state of the polymers showed X-ray diffraction patterns of periodic structures, which depend on the type of macromolecular chains: PEG showed a highly crystallized state in contrast to the slightly crystalline PDI molecules in the PDMS and PPG-based polymers. Photoconductivity upon ultraviolet excitation has been screened by noncontact microwave measurements, and the mobility of electrons has also been characterized based on the kinetic traces of radical anions on the PDI chromophores. The negligible optical absorption observed from the PDMS-based polymers revealed the lowest photocarrier generation yield among the prepared polymers. The observed low conductivity for the PDMS-based, most foldable polymers possibly results from a lower photo-charge generation yield and thermal fluctuations of the flexible PDMS chains. The PEG-based polymer marked the largest electron mobility of 0.2 cm 2 V 1 s 1 , reflecting the highly crystalline nature of the PEG chains.
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U2 - 10.1039/c7qm00616k
DO - 10.1039/c7qm00616k
M3 - Article
AN - SCOPUS:85051529602
VL - 2
SP - 718
EP - 729
JO - Materials Chemistry Frontiers
JF - Materials Chemistry Frontiers
SN - 2052-1537
IS - 4
ER -