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Peer-reviewedCC BY-NC-ND 4.0ACS Omega

Intramolecular Long-Range Photoinduced Electron Transfer Using π-Way of a Step-π-Conjugated Polymer

  • Daisuke Kitayama1
  • Kazuki Takeuchi1
  • Akari Terada1
  • Shota Shimaoka1
  • Hao-xuan Guo1
  • Hiroyuki Aota1
  1. 1Kansai University , Suita , ,
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Abstract

Photoinduced electron transfer (PET) along a π-scaffold with breaks remains poorly understood. To address this, we showed that a step-π-conjugated polymer (SPP)─made of alternating pyrrole rings and a single sp3 carbon─enables fast PET through its backbone. In this system, fluorescence quenching occurred when a perylene (Pe) donor was photoexcited in the presence of an anthraquinone (AQ) acceptor. To clarify the quenching mechanism, we considered four possibilities: (i) long-range (pseudo) through-bond PET, (ii) intermolecular through-space PET, (iii) short-range PET (through-space and through-bond), and (iv) intramolecular through-space PET. To systematically test which process dominated, we synthesized three polymers: water-soluble SPP, amphiphilic SPP, and poly(methacrylic acid) sodium salt (PMANa), which lacks π-conjugation. The fluorescence data of these polymers indicate that long-range (pseudo) through-bond PET is the main mechanism in the SPP system. Moreover, femtosecond transient absorption spectroscopy reveals a Pe radical cation (Pe•+) and AQ radical anion (AQ•–), confirming charge separation through the step-π-conjugated backbone. The PET (kET) and charge recombination (kCR) rate constants for RDA ≈ 1.8 nm are estimated to be kET > 2 × 1012 s–1 and kCR ≈ 1011 s–1 order, respectively. Thus, SPP enables long-range, fast PFT via a new π-way mechanism.

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Cite

BibTeXRIS
BibTeX
@article{kitayama2026intramolecular,
  title = {{Intramolecular Long-Range Photoinduced Electron Transfer Using π-Way of a Step-π-Conjugated Polymer}},
  author = {Daisuke Kitayama and Kazuki Takeuchi and Akari Terada and Shota Shimaoka and Hao-xuan Guo and Hiroyuki Aota},
  journal = {ACS Omega},
  year = {2026},
  month = oct,
  doi = {10.1021/acsomega.6c06841},
  url = {https://pubs.acs.org/acsodf/article/11/42/65145/5451782/Intramolecular-Long-Range-Photoinduced-Electron},
  note = {CC BY-NC-ND 4.0},
}
RIS
TY  - JOUR
TI  - Intramolecular Long-Range Photoinduced Electron Transfer Using π-Way of a Step-π-Conjugated Polymer
AU  - Daisuke Kitayama
AU  - Kazuki Takeuchi
AU  - Akari Terada
AU  - Shota Shimaoka
AU  - Hao-xuan Guo
AU  - Hiroyuki Aota
PY  - 2026
DA  - 2026/10/15
JO  - ACS Omega
DO  - 10.1021/acsomega.6c06841
UR  - https://pubs.acs.org/acsodf/article/11/42/65145/5451782/Intramolecular-Long-Range-Photoinduced-Electron
AB  - Photoinduced electron transfer (PET) along a π-scaffold with breaks remains poorly understood. To address this, we showed that a step-π-conjugated polymer (SPP)─made of alternating pyrrole rings and a single sp3 carbon─enables fast PET through its backbone. In this system, fluorescence quenching occurred when a perylene (Pe) donor was photoexcited in the presence of an anthraquinone (AQ) acceptor. To clarify the quenching mechanism, we considered four possibilities: (i) long-range (pseudo) through-bond PET, (ii) intermolecular through-space PET, (iii) short-range PET (through-space and through-bond), and (iv) intramolecular through-space PET. To systematically test which process dominated, we synthesized three polymers: water-soluble SPP, amphiphilic SPP, and poly(methacrylic acid) sodium salt (PMANa), which lacks π-conjugation. The fluorescence data of these polymers indicate that long-range (pseudo) through-bond PET is the main mechanism in the SPP system. Moreover, femtosecond transient absorption spectroscopy reveals a Pe radical cation (Pe•+) and AQ radical anion (AQ•–), confirming charge separation through the step-π-conjugated backbone. The PET (kET) and charge recombination (kCR) rate constants for RDA ≈ 1.8 nm are estimated to be kET > 2 × 1012 s–1 and kCR ≈ 1011 s–1 order, respectively. Thus, SPP enables long-range, fast PFT via a new π-way mechanism.
SN  - 2470-1343
ER  -