RESUMEN
Zr(iv) metal-organic frameworks (MOFs) UiO-68 and PCN-57, containing triphenylene dicarboxylate (TPDC) and tetramethyl-triphenylene dicarboxylate (TTDC) linkers, respectively, were doped with an H-shaped tetracarboxylate linker that contains a [2]rotaxane molecular shuttle. The new MOFs, UWDM-8 and UWDM-9, contain a [2]rotaxane crossbar spanning the tetrahedral cavities of the fcu topology while the octahedral cavities remain empty. 13C solid-state NMR (SSNMR) spectra and solution 1H NMR spectra verified that the [2]rotaxanes were included as designed. Variable-temperature (VT) cross polarization (CP) magic-angle spinning (MAS) 13C SSNMR was used to explore the translational motion of the macrocyclic ring in both MOFs. The SSNMR results clearly show that the structure of the linker (TPDCvs.TTDC) affects the shuttling rate of the macrocyclic ring, although questions remain as to how rotation of the central phenylene unit of the strut might also affect the motion of the macrocycle.
RESUMEN
Methacrylated lignin was reacted with PH3(g) to prepare a phosphorus rich bio-based polymer containing PH/PH2 functional groups, which were converted to tertiary phosphine units via the phosphane-ene reaction. This represents a straightforward method for the upconversion of low-value biomass waste to useful inorganic polymer with potential utility in metal scavenging applications.
Asunto(s)
Lignina/química , Metales/química , Fosfinas/química , BiomasaRESUMEN
A [2]rotaxane linker was synthesized which combines an H-shaped axle containing four 3-carboxyphenyl groups and a macrocyclic wheel with two 4-pyridyl groups. Metal-organic framework materials were prepared with CuII and ZnII ions X-ray structures show that the materials contain unique frameworks that are threaded solely due to the interpenetrated nature of the linker.
RESUMEN
A series of [2]rotaxane molecular shuttles was prepared containing a dibenzo[24]crown-8 (DB24C8) wheel and a rigid H-shaped axle with varying track lengths between recognition sites; from 7.4 to 20.3 Å as defined by 1-4 phenyl rings or a naphthyl group. The rate of shuttling was measured by variable temperature 1H NMR spectroscopy for neutral compounds and EXSY experiments for dicationic species. The rates were found to be independent of the length of the axle, except when the distance between the two recognition sites might be short enough (n = 1) to allow the crown ether to simultaneously interact with both recognition sites providing a short-cut mechanism which could lower the energy barrier. This notion is supported by DFT calculations and solid-state characterization of model compounds that mimic possible transition states.