Ferrocene-Based Conjugated Microporous Polymers Derived from Yamamoto Coupling for Gas Storage and Dye Removal.

Conjugated microporous polymers (CMPs) have conjugated skeleton and permanent porosity, and exhibit huge potential in developing novel functional materials for resolving the challenging energy and environment issues. Metal-containing CMPs often exhibited unique properties. In the present manuscript, ferrocene-based conjugated microporous polymers (FcCMPs) were designed and synthesized with 1,1'-dibromoferrocene and 5,10,15,20-Tetrakis(4- bromophenyl) porphyrin (FcCMP-1) or Tetra (p-bromophenyl) methane (FcCMP-2) as building units via Yamamoto coupling. FcCMPs were amorphous, and exhibited excellent thermal and physicochemical stability. The BET surface area of FcCMP-1 and FcCMP-2 was 638 m2/g and 422 m2/g, respectively. In comparison with FcCMP-2, FcCMP-1 displayed better gas storage capacity due to higher porosity. FcCMPs were also used as an adsorbent for removal of methyl violet from aqueous solution, and exhibited excellent adsorption properties due to the interaction between electron-rich conjugated structure of the polymers and methyl violet with cationic groups. Moreover, FcCMPs could be extracted and regenerated by an eluent and then re-used for high efficient removal of methyl violet.

Synthesis, characterization and magnetic properties of hollow microspheres with micro-mesoporous shells assembled from cobalt-based ferrocenyl coordination polymers.

Hollow magnetic microspheres with micro-mesoporous shells were constructed with layered cobalt-based ferrocenyl coordination polymers (Co-Fc-HCPS) through a one-step Ostwald ripening process. The diameters of microspheres and corresponding cavities were controlled in the range of several microns by tuning the reaction time and reactant concentration, which would attribute the microspheres with high loading, and enhanced mass diffusion and transfer efficiency. The high crystallinity of hollow microspheres allowed determination of the crystal structure of cobalt-based ferrocenyl coordination polymer, which crystallized in Brucite-type layered structure with the formula of Co(4)(OH)(4)(FcDC)(2), (H(2)FcDC=1,1'-ferrocenedicarboxylic acid), by combination of powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDX), element analysis (EA), and Fourier transform infrared spectroscopy (FT-IR). N(2) adsorption/desorption investigation revealed the existence of both mesopores around 3.81 nm and micropores of ca. 1 nm in the shells. The hollow microspheres exhibited spin-canted antiferromagnetism with weak ferromagnetic ordering below ~52 K, which showed a remanent magnetization (Mr) of 1.0 µ(B) and a large coercive field (Hc) of 5 kOe at 7 K.