Molecular Curvature Enables Tubular π-Stacked Pathways in Three-Dimensional Conductive Metal-Organic Frameworks
Abstract
Conductive metal-organic frameworks (MOFs) are commonly constructed from planar aromatic ligands, whose geometries favor conventional π-stacking arrangements. However, intrinsically twisted ligands offer an alternative geometric approach to directing aromatic packing and constructing unconventional framework architectures. Here, we employ intrinsically twisted, butterfly-shaped dibenzo[g,p]chrysene-2,3,6,7,10,11,14,15-octaol (DBC) ligands to construct a series of lanthanide MOFs. Single-crystal X-ray diffraction reveals an interpenetrated three-dimensional framework in which π-π interactions between the aromatic fragments generate axially extended tubular π-stacked pathways, alongside one-dimensional channels rich in hydrogen-bonding sites. Lanthanide substitution preserves the overall tubular framework topology while modulating aromatic stacking distances and local pore environments. PrDBC single crystals exhibit mixed electron-proton transport, with electron and proton conductivities reaching 1.62 x 10-3 and 4.37 x 10-4 S cm-1, respectively, at 338 K and 30% relative humidity. This work highlights molecular curvature as a structural design strategy for constructing three-dimensional conductive MOFs that integrate tubular aromatic stacks with tunable pore environments for mixed electron-proton transport.
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BibTeX
@misc{li2026molecular,
title = {{Molecular Curvature Enables Tubular π-Stacked Pathways in Three-Dimensional Conductive Metal-Organic Frameworks}},
author = {Weishan Li and Jia-Xiang Zhang and Tongyang Zhao and Hao Chen and Tianyang Chen and Ze-Fan Yao and Jin-Hu Dou},
howpublished = {arXiv},
year = {2026},
month = nov,
doi = {10.48550/arxiv.2611.02945},
eprint = {2611.02945},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2611.02945},
}
RIS
TY - UNPB
TI - Molecular Curvature Enables Tubular π-Stacked Pathways in Three-Dimensional Conductive Metal-Organic Frameworks
AU - Weishan Li
AU - Jia-Xiang Zhang
AU - Tongyang Zhao
AU - Hao Chen
AU - Tianyang Chen
AU - Ze-Fan Yao
AU - Jin-Hu Dou
PY - 2026
DA - 2026/11/02
PB - arXiv
DO - 10.48550/arxiv.2611.02945
UR - https://arxiv.org/abs/2611.02945
AB - Conductive metal-organic frameworks (MOFs) are commonly constructed from planar aromatic ligands, whose geometries favor conventional π-stacking arrangements. However, intrinsically twisted ligands offer an alternative geometric approach to directing aromatic packing and constructing unconventional framework architectures. Here, we employ intrinsically twisted, butterfly-shaped dibenzo[g,p]chrysene-2,3,6,7,10,11,14,15-octaol (DBC) ligands to construct a series of lanthanide MOFs. Single-crystal X-ray diffraction reveals an interpenetrated three-dimensional framework in which π-π interactions between the aromatic fragments generate axially extended tubular π-stacked pathways, alongside one-dimensional channels rich in hydrogen-bonding sites. Lanthanide substitution preserves the overall tubular framework topology while modulating aromatic stacking distances and local pore environments. PrDBC single crystals exhibit mixed electron-proton transport, with electron and proton conductivities reaching 1.62 x 10-3 and 4.37 x 10-4 S cm-1, respectively, at 338 K and 30% relative humidity. This work highlights molecular curvature as a structural design strategy for constructing three-dimensional conductive MOFs that integrate tubular aromatic stacks with tunable pore environments for mixed electron-proton transport.
ER -