Vinylene-Linked Covalent Organic Frameworks with Heteropore-Tuned Compact Motifs for Boosting Spin-Spin Interactions
5 affiliations
- 1School of Chemistry and Chemical Engineering, State Key Laboratory of Synergistic Chem-Bio Synthesis
- 2Shanghai Jiao Tong University
- 3Frontiers Science Center for Transformative Molecules
- 4Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University
- 5Yunnan Advanced Elastomer Industry Innovation Research Institute Co., Ltd
Abstract
The rich porosity of covalent organic frameworks (COFs) renders them abundant mass transport channels and easily accessible active sites. However, relatively low compact skeletons of COFs are unfavorable for in-plane and out-of-plane electron spin coupling. Herein, we report a new π-extended polyheterocyclic aromatic derivative by fusing three 2,3-dimethylpyrazine moieties to a triphenylene core, which serves as a D3h-symmetric hexatopic monomer to undergo Knoevenagel condensation smoothly with linear dialdehyde aromatics, forming a novel type of two-dimensional vinylene-linked COFs. Their three pairs of vinylene linkages at the adjacent positions of each disc-like vertex with seven fused aromatic rings tend to geometrically constrain the orientation and alleviate the congestion in the chain growth process, leading to in-plane compact Kagome motifs, alternatively patterned with the pseudohexagonal micropore and triangular ultramicropore. The as-prepared COFs enable efficient uptake of iodine molecules and generate a strong charge transfer complex at the pyridine nitrogen atoms, as revealed by electron paramagnetic resonance (EPR) signals. The resultant radicals, densely confined in the highly ordered reticular skeletons, allow for unidirectional electron spin alignment, which further induces a typical ferromagnetic phase transition, delivering metal-free magnetism with a tunable intensity through the compacting of the backbones of COFs.
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BibTeX
@misc{meng2026vinylenelinked,
title = {{Vinylene-Linked Covalent Organic Frameworks with Heteropore-Tuned Compact Motifs for Boosting Spin-Spin Interactions}},
author = {Fancheng Meng and Jinyu Zhao and Jindong Wu and Xuanzi Ye and Xiaomeng Li and Kaiyue Jiang and Bai Xue and Xiaodong Zhuang and Jianneng Li and Kui Yang and Fan Zhang},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010818/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010818/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Vinylene-Linked Covalent Organic Frameworks with Heteropore-Tuned Compact Motifs for Boosting Spin-Spin Interactions
AU - Fancheng Meng
AU - Jinyu Zhao
AU - Jindong Wu
AU - Xuanzi Ye
AU - Xiaomeng Li
AU - Kaiyue Jiang
AU - Bai Xue
AU - Xiaodong Zhuang
AU - Jianneng Li
AU - Kui Yang
AU - Fan Zhang
PY - 2026
DA - 2026/10/22
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010818/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010818/v1
AB - The rich porosity of covalent organic frameworks (COFs) renders them abundant mass transport channels and easily accessible active sites. However, relatively low compact skeletons of COFs are unfavorable for in-plane and out-of-plane electron spin coupling. Herein, we report a new π-extended polyheterocyclic aromatic derivative by fusing three 2,3-dimethylpyrazine moieties to a triphenylene core, which serves as a D3h-symmetric hexatopic monomer to undergo Knoevenagel condensation smoothly with linear dialdehyde aromatics, forming a novel type of two-dimensional vinylene-linked COFs. Their three pairs of vinylene linkages at the adjacent positions of each disc-like vertex with seven fused aromatic rings tend to geometrically constrain the orientation and alleviate the congestion in the chain growth process, leading to in-plane compact Kagome motifs, alternatively patterned with the pseudohexagonal micropore and triangular ultramicropore. The as-prepared COFs enable efficient uptake of iodine molecules and generate a strong charge transfer complex at the pyridine nitrogen atoms, as revealed by electron paramagnetic resonance (EPR) signals. The resultant radicals, densely confined in the highly ordered reticular skeletons, allow for unidirectional electron spin alignment, which further induces a typical ferromagnetic phase transition, delivering metal-free magnetism with a tunable intensity through the compacting of the backbones of COFs.
ER -