Deciphering Dynamic Self-Healing for Crystallinity Control in β-Ketoenamine-Linked Covalent Organic Frameworks
Abstract
Covalent organic frameworks derived from triformylphloroglucinol (Tp-COFs) represent a prominent branch of COFs due to their high potential in separation, energy storage, and optoelectronics. However, the development of Tp-COFs is often hindered by limited crystallinity, resulting from the low reversibility of β-ketoenamine bond formation. In this study, we report an unprecedented dynamic self-healing mechanism during Tp-COF formation, arising from a reversible Michael-addition-elimination (MAE) process. Building on this insight, a modulator-mediated MAE pathway is further established for crystallinity control. As a representative example, Tp-COF-1 synthesized via this strategy (Tp-COF-1(H)) forms well-defined columnar crystals with domain sizes up to 20 µm × 2 µm, and exhibits significantly improved structural order, as evidenced by a sharper powder x-ray diffraction (PXRD) peak (full width at half maximum: 0.44° vs. 0.74°) and a higher specific surface area (1314 vs. 647 m2 g−1), compared to Tp-COF-1 synthesized by the conventional method (Tp-COF-1(O)). Moreover, optical pump-terahertz probe spectroscopy reveals a photoexcited charge-carrier mobility of 10.84 cm2 V−1 s−1 for Tp-COF-1(H), which is 1.77 times higher than that of Tp-COF-1(O). These findings identify dynamic self-healing process via MAE as a key mechanism for governing Tp-COF crystallization toward highly ordered Tp-COFs for optoelectronic applications.
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BibTeX
@article{qiu2026deciphering,
title = {{Deciphering Dynamic Self-Healing for Crystallinity Control in β-Ketoenamine-Linked Covalent Organic Frameworks}},
author = {Fan Qiu and Lei Gao and Yubin Fu and Sankalpa N Panda and Xing Su and Ya Lu and Mei‐mei Zhang and Mischa Bonn and Paolo Samorì and Yuqiao Wang and Xin Zhao and Shun‐qi Xu},
journal = {Angewandte Chemie International Edition},
year = {2026},
month = sep,
doi = {10.1002/anie.5409854},
url = {https://univoak.hal.science/hal-05851358v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Deciphering Dynamic Self-Healing for Crystallinity Control in β-Ketoenamine-Linked Covalent Organic Frameworks
AU - Fan Qiu
AU - Lei Gao
AU - Yubin Fu
AU - Sankalpa N Panda
AU - Xing Su
AU - Ya Lu
AU - Mei‐mei Zhang
AU - Mischa Bonn
AU - Paolo Samorì
AU - Yuqiao Wang
AU - Xin Zhao
AU - Shun‐qi Xu
PY - 2026
DA - 2026/09/18
JO - Angewandte Chemie International Edition
DO - 10.1002/anie.5409854
UR - https://univoak.hal.science/hal-05851358v1
AB - Covalent organic frameworks derived from triformylphloroglucinol (Tp-COFs) represent a prominent branch of COFs due to their high potential in separation, energy storage, and optoelectronics. However, the development of Tp-COFs is often hindered by limited crystallinity, resulting from the low reversibility of β-ketoenamine bond formation. In this study, we report an unprecedented dynamic self-healing mechanism during Tp-COF formation, arising from a reversible Michael-addition-elimination (MAE) process. Building on this insight, a modulator-mediated MAE pathway is further established for crystallinity control. As a representative example, Tp-COF-1 synthesized via this strategy (Tp-COF-1(H)) forms well-defined columnar crystals with domain sizes up to 20 µm × 2 µm, and exhibits significantly improved structural order, as evidenced by a sharper powder x-ray diffraction (PXRD) peak (full width at half maximum: 0.44° vs. 0.74°) and a higher specific surface area (1314 vs. 647 m2 g−1), compared to Tp-COF-1 synthesized by the conventional method (Tp-COF-1(O)). Moreover, optical pump-terahertz probe spectroscopy reveals a photoexcited charge-carrier mobility of 10.84 cm2 V−1 s−1 for Tp-COF-1(H), which is 1.77 times higher than that of Tp-COF-1(O). These findings identify dynamic self-healing process via MAE as a key mechanism for governing Tp-COF crystallization toward highly ordered Tp-COFs for optoelectronic applications.
SN - 1433-7851
SN - 1521-3773
ER -