TY - JOUR
T1 - Self-assembly of metal-organic polyhedra into supramolecular polymers with intrinsic microporosity
AU - Carné-Sánchez, Arnau
AU - Craig, Gavin A.
AU - Larpent, Patrick
AU - Hirose, Takashi
AU - Higuchi, Masakazu
AU - Kitagawa, Susumu
AU - Matsuda, Kenji
AU - Urayama, Kenji
AU - Furukawa, Shuhei
PY - 2018
Y1 - 2018
N2 - Designed porosity in coordination materials often relies on highly ordered crystalline networks, which provide stability upon solvent removal. However, the requirement for crystallinity often impedes control of higher degrees of morphological versatility, or materials processing. Herein, we describe a supramolecular approach to the synthesis of amorphous polymer materials with controlled microporosity. The strategy entails the use of robust metal-organic polyhedra (MOPs) as porous monomers in the supramolecular polymerization reaction. Detailed analysis of the reaction mechanism of the MOPs with imidazole-based linkers revealed the polymerization to consist of three separate stages: nucleation, elongation, and cross-linking. By controlling the self-assembly pathways, we successfully tuned the resulting macroscopic form of the polymers, from spherical colloidal particles to colloidal gels with hierarchical porosity. The resulting materials display distinct microporous properties arising from the internal cavity of the MOPs. This synthetic approach could lead to the fabrication of soft, flexible materials with permanent porosity. Porosity in metal-organic materials typically relies on highly ordered crystalline networks, which hinders material processing and morphological control. Here, the authors use metal-organic polyhedra as porous monomers in supramolecular polymerization to produce colloidal spheres and gels with intrinsic microporosity.
AB - Designed porosity in coordination materials often relies on highly ordered crystalline networks, which provide stability upon solvent removal. However, the requirement for crystallinity often impedes control of higher degrees of morphological versatility, or materials processing. Herein, we describe a supramolecular approach to the synthesis of amorphous polymer materials with controlled microporosity. The strategy entails the use of robust metal-organic polyhedra (MOPs) as porous monomers in the supramolecular polymerization reaction. Detailed analysis of the reaction mechanism of the MOPs with imidazole-based linkers revealed the polymerization to consist of three separate stages: nucleation, elongation, and cross-linking. By controlling the self-assembly pathways, we successfully tuned the resulting macroscopic form of the polymers, from spherical colloidal particles to colloidal gels with hierarchical porosity. The resulting materials display distinct microporous properties arising from the internal cavity of the MOPs. This synthetic approach could lead to the fabrication of soft, flexible materials with permanent porosity. Porosity in metal-organic materials typically relies on highly ordered crystalline networks, which hinders material processing and morphological control. Here, the authors use metal-organic polyhedra as porous monomers in supramolecular polymerization to produce colloidal spheres and gels with intrinsic microporosity.
U2 - 10.1038/s41467-018-04834-0
DO - 10.1038/s41467-018-04834-0
M3 - Article
C2 - 30002378
SN - 2041-1723
VL - 9
JO - Nature Communications
JF - Nature Communications
ER -