The curious case of COF-300: One framework, Seventeen years of structural reinterpretation
Abstract
Few frameworks have changed the meaning of their own structural description as profoundly as COF-300. Over seventeen years, this archetypal three-dimensional covalent organic framework has evolved from a powder-derived interpenetrated model into a condition-dependent structural landscape. Successive studies revealed that conserved covalent connectivity can accommodate different interpenetration states, pronounced geometrical distortion, guest-selected conformers and large-amplitude breathing through coupled linker rotation, node deformation and interframework displacement. The structural problem subsequently expanded beyond the unit cell: crystal size, facets, local disorder, surfaces and composition alter mechanical response, while amorphous polymers, ordered molecular intermediates, classical growth and oriented attachment expose multiple routes by which crystallinity emerges. Recent advances go further, enabling crystallization trajectories, defects and even covalent linkages to be deliberately manipulated without necessarily erasing crystallographic identity. COF-300 is therefore better understood not through a single CIF, but as a history- and environment-dependent ensemble of states connected by kinetic pathways and energetic barriers. Its seventeen-year evolution reframes a broader challenge for dynamic reticular materials: structural determination must progress toward structural cartography, and reticular design from programming connectivity toward programming landscapes—the accessible states, transitions and histories through which a crystal acquires its behaviour.
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BibTeX
@misc{irie2026curious,
title = {{The curious case of COF-300: One framework, Seventeen years of structural reinterpretation}},
author = {Tsukasa Irie and Saikat Das and Yuichi Negishi},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010594/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010594/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - The curious case of COF-300: One framework, Seventeen years of structural reinterpretation
AU - Tsukasa Irie
AU - Saikat Das
AU - Yuichi Negishi
PY - 2026
DA - 2026/10/16
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010594/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010594/v1
AB - Few frameworks have changed the meaning of their own structural description as profoundly as COF-300. Over seventeen years, this archetypal three-dimensional covalent organic framework has evolved from a powder-derived interpenetrated model into a condition-dependent structural landscape. Successive studies revealed that conserved covalent connectivity can accommodate different interpenetration states, pronounced geometrical distortion, guest-selected conformers and large-amplitude breathing through coupled linker rotation, node deformation and interframework displacement. The structural problem subsequently expanded beyond the unit cell: crystal size, facets, local disorder, surfaces and composition alter mechanical response, while amorphous polymers, ordered molecular intermediates, classical growth and oriented attachment expose multiple routes by which crystallinity emerges. Recent advances go further, enabling crystallization trajectories, defects and even covalent linkages to be deliberately manipulated without necessarily erasing crystallographic identity. COF-300 is therefore better understood not through a single CIF, but as a history- and environment-dependent ensemble of states connected by kinetic pathways and energetic barriers. Its seventeen-year evolution reframes a broader challenge for dynamic reticular materials: structural determination must progress toward structural cartography, and reticular design from programming connectivity toward programming landscapes—the accessible states, transitions and histories through which a crystal acquires its behaviour.
ER -