One-Dimensional van der Waals Porous Fibrils Assembled from Metal–Organic Polyhedra
Journal
Journal of the American Chemical Society
Journal Volume
148
Journal Issue
12
Start Page
12946
End Page
12958
ISSN
0002-7863
1520-5126
Date Issued
2026-03-19
Author(s)
Miyata, Ayana
Tokuda, Shun
Kuzumoto, Mako
Lee, Guan-Sian
Yamashita, Masataka
Nishiguchi, Taichi
Negoro, Masaki
Pauw, Brian R.
Kanamori, Kazuyoshi
Urayama, Kenji
Sugimoto, Kunihisa
Furukawa, Shuhei
Abstract
Supramolecular systems exhibit collective functions that emerge from the hierarchical assembly of individual molecular building blocks. Metal–organic polyhedra (MOPs) are a class of functional supramolecular architectures with well-defined molecular geometry and an intrinsic cavity. In recent years, considerable progress has been made in assembling MOPs into extended networks to create porous solids. However, most reported MOP assemblies are limited to three-dimensional networks, which, owing to their high-dimensional connectivity, hinder effective stress dissipation and render them brittle under mechanical stress. Here, we report the one-dimensional (1D) self-assembly of MOPs into supramolecular polymeric aerogels that combine permanent microporosity with exceptional mechanical flexibility. The reaction between amino acid-functionalized naphthalenediimide (NDI) linkers and copper salts led to the synthesis of octahedral copper-based MOPs, followed by their spontaneous self-assembly to form supramolecular gels. The corresponding aerogels converted from the gels possessed uniform 1D fibrillar networks (14.8 ± 2.2 nm in width) with intrinsic microporosity derived from individual MOP cavities. The aerogel endured 87% compressive strain without fracture, demonstrating distinct ductility. Furthermore, these fibrils in the supramolecular gels were converted to crystals after 2 weeks. Single-crystal X-ray diffraction revealed that MOPs are arranged via face-to-face interaction between octahedral MOPs to form a 1D helical chain structure. An analysis of the self-assembly process using Hansen solubility parameters unveiled that solvent conditions with high polarity and low dispersion interaction drive the formation of anisotropic assemblies. This work provides a new strategy for tailoring the mechanical properties of supramolecular materials through dimensional control of their assemblies.
Publisher
American Chemical Society (ACS)
Type
journal article