Supramolecular structures and metal-organic frameworks based on metal dipyrrin building blocks.

摘要

Metal dipyrrin complexes have the potential to be incorporated into a variety of supramolecular systems and metal-organic frameworks (MOFs). Despite their potential, limited work has been done to study simple meso-substituted dipyrrin metal complexes for their use in supramolecular systems; therefore, dipyrrin ligands and metal complexes have been synthesized and studied. Metal dipyrrin complexes were prepared containing copper(II), iron(III), or cobalt(III) metal centers. Phenylacetylene spacers and perfluorophenyl groups were introduced and their effects were studied.; During the preparation of certain dipyrrins, new alpha-substituted dipyrrin ligands were identified and their metal-coordination was explored. Also in the preparation of certain dipyrrins, a wide variety of supramolecular structures containing heteroleptic copper(II) dipyrrin complexes emerged, ranging from one-dimensional coordination polymers to discrete supramolecular hexagons. One very unique structure emerged consisting of both discrete supramolecular hexagons and double-helical polymer chains in the same crystalline framework. The materials were characterized by various methods including single crystal X-ray diffraction. Studies on their topology and their structural driving forces such as F-F interactions were carried out.; Finally, a series of MOFs containing cobalt(III) and iron(III) metal dipyrrin complexes and silver(I) salts were prepared. The materials were primarily characterized by X-ray diffraction. Once again a wide variety of topologies emerged, ranging from two-dimensional hexagonal sheets to elaborate three-dimensional topologies. One particular combination of a dipyrrin complex and silver(I) salt formed a chiral MOF. Mixed-metal MOFs were also prepared, as well as MOFs containing large dipyrrin building blocks. The counterion was shown to template the formation of the frameworks; therefore anion templating and anion exchange studies were performed.