Self-Assembly of Heteroleptic [Cu(dipyrrinato)(hfacac)] Complexes Directed by Fluorine−Fluorine Interactions

Heteroleptic copper(II) complexes were synthesized from three
different meso-substituted pyridyl- and quinoline-dipyrrinato ligands
(3-pyrdpm, 3-quindpm, and 4-quindpm). Metal complexes were
prepared with both acetylacetonate (acac) and hexafluoroacetylactonate (hfacac) ancillary ligands. The complexes undergo a self-complementary self-assembly process upon crystallization to
generate a range of solid-state topologies including one-dimensional
coordination polymers and discrete hexameric rings. The self-assembly of these molecular aggregates is driven by metal−ligand
bonding, but is also modulated by fluorine−fluorine interactions.
Perfluorination of the spectator ligand tends to generate more
compact structures, which is attributed to aggregation of the
perfluoromethyl groups. The results presented here demonstrate
that fluorine−fluorine contacts can be used to modulate supramolecular structures in the solid state.