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PreprintCC BY-NCChemRxiv

Oxygen-Necessitated Dissociation of Photoinduced Ground-State Charge-Transfer Complexes for Open-Air Synthesis of Block and Graft Copolymers

  • Runyang Miao1,2,3
  • Jing Chen1,2,3
  • Aoyuan Cheng1,2,3
  • Hongping Liu1,2,3
  • Baicheng Zhang1,2
  • Taiyuan Li1,2,3
  • Guangjian Cheng1,2,3
  • Wenhuan Huang1,2
  • Jun Jiang1,2
  • Yi Luo1,2
  • Guoqing Zhang1,2,3
  1. 1Hefei National Research Center for Physical Sciences at the Microscale
  2. 2University of Science and Technology of China
  3. 3Hefei National Laboratory
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Abstract

Molecular oxygen is universally regarded as an inhibitor of radical photopolymerization, necessitating rigorous deoxygenation and introducing obligatory induction periods. Here we report that a persistent photoinduced ground-state charge-transfer complex (PCTC), formed between a naphthalimide acceptor and a tertiary-amine donor, undergoes selective dissociation upon exposure to molecular oxygen. This oxygen-triggered activation releases a donor-derived radical cation while regenerating the acceptor, converting ambient O2 from an inhibitory species into a functional trigger for radical generation. The resulting photopolymerization proceeds without metal catalysts, or external initiators under open-air conditions. Because the tertiary-amine functionality is preserved at the polymer chain end, the system supports sequential photocontrolled chain extension, enabling the synthesis of block and graft copolymers. Extension to α-methylene amine-functionalized polymer backbones affords brush architectures that function as high-performance photocurable adhesives (lap-shear strength up to 20.38 MPa), exhibit robust electrical insulation, and permit rapid photo-patterning with micron resolution in open air. These findings establish an open-air photocuring platform that overturns the long-standing requirement for deoxygenation in industrial radical processing, offering a scalable, metal-free route to advanced polymer materials in ambient manufacturing environments.

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Cite

BibTeXRIS
BibTeX
@misc{miao2026oxygennecessitated,
  title = {{Oxygen-Necessitated Dissociation of Photoinduced Ground-State Charge-Transfer Complexes for Open-Air Synthesis of Block and Graft Copolymers}},
  author = {Runyang Miao and Jing Chen and Aoyuan Cheng and Hongping Liu and Baicheng Zhang and Taiyuan Li and Guangjian Cheng and Wenhuan Huang and Jun Jiang and Yi Luo and Guoqing Zhang},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008322/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008322/v1},
  note = {CC BY-NC},
}
RIS
TY  - UNPB
TI  - Oxygen-Necessitated Dissociation of Photoinduced Ground-State Charge-Transfer Complexes for Open-Air Synthesis of Block and Graft Copolymers
AU  - Runyang Miao
AU  - Jing Chen
AU  - Aoyuan Cheng
AU  - Hongping Liu
AU  - Baicheng Zhang
AU  - Taiyuan Li
AU  - Guangjian Cheng
AU  - Wenhuan Huang
AU  - Jun Jiang
AU  - Yi Luo
AU  - Guoqing Zhang
PY  - 2026
DA  - 2026/09/04
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008322/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008322/v1
AB  - Molecular oxygen is universally regarded as an inhibitor of radical photopolymerization, necessitating rigorous deoxygenation and introducing obligatory induction periods. Here we report that a persistent photoinduced ground-state charge-transfer complex (PCTC), formed between a naphthalimide acceptor and a tertiary-amine donor, undergoes selective dissociation upon exposure to molecular oxygen. This oxygen-triggered activation releases a donor-derived radical cation while regenerating the acceptor, converting ambient O2 from an inhibitory species into a functional trigger for radical generation. The resulting photopolymerization proceeds without metal catalysts, or external initiators under open-air conditions. Because the tertiary-amine functionality is preserved at the polymer chain end, the system supports sequential photocontrolled chain extension, enabling the synthesis of block and graft copolymers. Extension to α-methylene amine-functionalized polymer backbones affords brush architectures that function as high-performance photocurable adhesives (lap-shear strength up to 20.38 MPa), exhibit robust electrical insulation, and permit rapid photo-patterning with micron resolution in open air. These findings establish an open-air photocuring platform that overturns the long-standing requirement for deoxygenation in industrial radical processing, offering a scalable, metal-free route to advanced polymer materials in ambient manufacturing environments.
ER  -