Supramolecular chemistry is a rapidly growing field of research concerned with the construction of molecular assemblies held together by noncovalent interactions. [1,2] Forces such as hydrogen bonding, p-p stacking, and metalligand coordination have been extensively used in the synthesis of supramolecular structures. These assemblies are anticipated to find utility as new materials with novel catalytic, magnetic, electronic, and optical properties. [3][4][5][6] Within the realm of supramolecular complexes that utilize metal-ligand interactions, both discrete molecular species and coordination polymers have been investigated. We are aware of only one case in which a reaction has yielded both a discrete complex and an extended polymeric structure from the same building block.[7] However, we know of no examples in which these two general topologies were found to co-exist in a stable crystalline solid. Herein, we report the synthesis of a self-assembling, self-complementary metal complex that forms a supramolecular hexagon and a double-helical coordination polymer within a single crystalline lattice. Furthermore, it is proposed that aggregation of fluorine substituents is a key feature in directing the formation of this surprising example of supramolecular assembly.We have previously described heteroleptic copper(ii) complexes with dipyrromethene (dipyrrin) ligands [8] that can form self-complementary, one-dimensional "zig-zag" coordination polymers.[9] These complexes consist of square-planar copper(ii) centers bound by one dipyrrin ligand and one acetylacetonate (acac) ligand. The dipyrrin ligand features a second donor site (pyridyl nitrogen atom) that coordinates to the axial position of a neighboring copper(ii) center, thereby generating an extended structure. In an effort to explore the features of these complexes that would alter the polymeric structure, modifications of the acac ligand were pursued. Instead of using Cu(acac) 2 as the copper source, Cu(hfacac) 2 (hfacac = hexafluoroacetononate) was utilized, which resulted in a heteroleptic metal complex with a "blocking" hfacac ligand (Scheme 1). This change in the spectator ligand was found to noticeably alter the complexation behavior and supramolecular assembly of the heteroleptic compound.The products of the reaction between the dipyrrin ligand (4-pyrdpm = 5-(4-pyridyl)dipyrromethene, 2) and Cu(hfacac) 2 were found to be dependent on the component stoichiometry (Scheme 1). In situ generation of 2 combined with an excess of Cu(hfacac) 2 results in the isolation of the Scheme 1. Scheme for the synthesis of 4-pyrdpm (2) and heteroleptic copper complexes (3 and 4).