Abstract
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.
Highlights
Designed porosity in coordination materials often relies on highly ordered crystalline networks, which provide stability upon solvent removal
We recently reported the synthesis of a highly stable cuboctahedral MOP based on a dirhodium paddlewheel motif, [Rh2(bdc)2]12 (Fig. 2, H2bdc = benzene-1,3dicarboxylic acid)[23]
To investigate the supramolecular polymerization process of the C12RhMOP molecules triggered by the addition of the ditopic ligand, Dynamic light scattering (DLS) experiments were used to observe the effect of the size of the steps employed in the stepwise addition of bix on the resulting size of the coordination polymer particles (CPP)-1 particles
Summary
Designed porosity in coordination materials often relies on highly ordered crystalline networks, which provide stability upon solvent removal. The DLS experiments illustrate the assembly process of the C12RhMOP molecules into polymers as driven by the ligand exchange reaction: upon stepwise addition of bix The composition of CPP-1 was determined by 1H-NMR spectroscopy subsequent to acid digestion of the particles, and found to be (C12RhMOP)(bix)[6] (MOP: bix = 1:6, Supplementary Figure 9).
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