RESUMEN
Pyrenes, as photoactive polycyclic aromatic hydrocarbons (PAHs), represent promising modules for the bottom-up assembly of functional nanostructures. Here, we introduce the synthesis of a family of pyrene derivatives peripherally functionalized with pyridin-4-ylethynyl termini and comprehensively characterize their self-assembly abilities on a smooth Ag(111) support by scanning tunneling microscopy. By deliberate selection of number and geometric positioning of the pyridyl-terminated substituents, two-dimensional arrays, one-dimensional coordination chains, and chiral, porous kagomé-type networks can be tailored. A comparison to phenyl-functionalized reference pyrenes, not supporting the self-assembly of ordered structures at low coverage, highlights the role of the pyridyl moieties for supramolecular crocheting and knitting. Furthermore, we demonstrate the selective spangling of pores in the two-dimensional pyrene assemblies by a distinct number of iodine atoms as guests by atomically resolved imaging and complementary X-ray photoelectron spectroscopy.
RESUMEN
Amino-functionalised metal-organic frameworks UiO-66 and -67 were post-synthetically modified with salicylaldehyde. A molybdenum complex was immobilised on the resulting materials. They were characterised by (13)C-MAS-NMR, XPS and PXRD to confirm immobilisation and stability. The immobilised complex is an active and reusable catalyst for olefin epoxidation with tert-butyl hydroperoxide (TBHP) as an oxidant. It is shown that the effective pore size, probed with Brunauer-Emmett-Teller (BET) surface area analysis and the number of amino groups affect the diffusion of reactants and products, as well as catalyst recycling.