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Mesoporous acridinium-based covalent organic framework for long-lived charge-separated exciton mediated photocatalytic [4+2] annulation

Ipsita Nath (UGent) , Jeet Chakraborty (UGent) , Kuber Singh Rawat (UGent) , Yanwei Ji (UGent) , Rundong Wang (UGent) , Korneel Molkens (UGent) , Nathalie De Geyter (UGent) , Rino Morent (UGent) , Veronique Van Speybroeck (UGent) , Pieter Geiregat (UGent) , et al.
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Abstract
Readily tuneable porosity and redox properties of covalent organic frameworks (COFs) result in highly customizable photocatalysts featuring extended electronic delocalization. However, fast charge recombination in COFs severely limits their photocatalytic activities. Herein a new mode of COF photocatalyst design strategy to introduce systematic trap states is programmed, which aids the formation and stabilization of long-lived charge-separated excitons. Installing cationic acridinium functionality in a pristine electron-rich triphenylamine COF via postsynthetic modification resulted in a semiconducting photocatalytic donor-acceptor dyad network that performed rapid and efficient oxidative Diels-Alder type [4+2] annulation of styrenes and alkynes to fused aromatic compounds under the atmospheric condition in good to excellent yields. Large mesopores of approximate to 4 nm diameter ensured efficient mass flow within the COF channel. It is confirmed that the catalytic performance of COF originates from the ultra-stable charge-separated excitons of 1.9 nm diameter with no apparent radiative charge-recombination pathway, endorsing almost a million times better photo-response and catalysis than the state-of-the-art.
Keywords
POROSITY, acridinium, charge separation, covalent organic framework, exciton, photocatalysis

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Citation

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MLA
Nath, Ipsita, et al. “Mesoporous Acridinium-Based Covalent Organic Framework for Long-Lived Charge-Separated Exciton Mediated Photocatalytic [4+2] Annulation.” ADVANCED MATERIALS, vol. 37, no. 1, 2025, doi:10.1002/adma.202413060.
APA
Nath, I., Chakraborty, J., Singh Rawat, K., Ji, Y., Wang, R., Molkens, K., … Van Der Voort, P. (2025). Mesoporous acridinium-based covalent organic framework for long-lived charge-separated exciton mediated photocatalytic [4+2] annulation. ADVANCED MATERIALS, 37(1). https://doi.org/10.1002/adma.202413060
Chicago author-date
Nath, Ipsita, Jeet Chakraborty, Kuber Singh Rawat, Yanwei Ji, Rundong Wang, Korneel Molkens, Nathalie De Geyter, et al. 2025. “Mesoporous Acridinium-Based Covalent Organic Framework for Long-Lived Charge-Separated Exciton Mediated Photocatalytic [4+2] Annulation.” ADVANCED MATERIALS 37 (1). https://doi.org/10.1002/adma.202413060.
Chicago author-date (all authors)
Nath, Ipsita, Jeet Chakraborty, Kuber Singh Rawat, Yanwei Ji, Rundong Wang, Korneel Molkens, Nathalie De Geyter, Rino Morent, Veronique Van Speybroeck, Pieter Geiregat, and Pascal Van Der Voort. 2025. “Mesoporous Acridinium-Based Covalent Organic Framework for Long-Lived Charge-Separated Exciton Mediated Photocatalytic [4+2] Annulation.” ADVANCED MATERIALS 37 (1). doi:10.1002/adma.202413060.
Vancouver
1.
Nath I, Chakraborty J, Singh Rawat K, Ji Y, Wang R, Molkens K, et al. Mesoporous acridinium-based covalent organic framework for long-lived charge-separated exciton mediated photocatalytic [4+2] annulation. ADVANCED MATERIALS. 2025;37(1).
IEEE
[1]
I. Nath et al., “Mesoporous acridinium-based covalent organic framework for long-lived charge-separated exciton mediated photocatalytic [4+2] annulation,” ADVANCED MATERIALS, vol. 37, no. 1, 2025.
@article{01JK89MPQJQZ99B1S8G6SK5V92,
  abstract     = {{Readily tuneable porosity and redox properties of covalent organic frameworks (COFs) result in highly customizable photocatalysts featuring extended electronic delocalization. However, fast charge recombination in COFs severely limits their photocatalytic activities. Herein a new mode of COF photocatalyst design strategy to introduce systematic trap states is programmed, which aids the formation and stabilization of long-lived charge-separated excitons. Installing cationic acridinium functionality in a pristine electron-rich triphenylamine COF via postsynthetic modification resulted in a semiconducting photocatalytic donor-acceptor dyad network that performed rapid and efficient oxidative Diels-Alder type [4+2] annulation of styrenes and alkynes to fused aromatic compounds under the atmospheric condition in good to excellent yields. Large mesopores of approximate to 4 nm diameter ensured efficient mass flow within the COF channel. It is confirmed that the catalytic performance of COF originates from the ultra-stable charge-separated excitons of 1.9 nm diameter with no apparent radiative charge-recombination pathway, endorsing almost a million times better photo-response and catalysis than the state-of-the-art.}},
  articleno    = {{2413060}},
  author       = {{Nath, Ipsita and Chakraborty, Jeet and Singh Rawat, Kuber and Ji, Yanwei and Wang, Rundong and Molkens, Korneel and De Geyter, Nathalie and Morent, Rino and Van Speybroeck, Veronique and Geiregat, Pieter and Van Der Voort, Pascal}},
  issn         = {{0935-9648}},
  journal      = {{ADVANCED MATERIALS}},
  keywords     = {{POROSITY,acridinium,charge separation,covalent organic framework,exciton,photocatalysis}},
  language     = {{eng}},
  number       = {{1}},
  pages        = {{11}},
  title        = {{Mesoporous acridinium-based covalent organic framework for long-lived charge-separated exciton mediated photocatalytic [4+2] annulation}},
  url          = {{http://doi.org/10.1002/adma.202413060}},
  volume       = {{37}},
  year         = {{2025}},
}

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