Four planar tripyridyl ligands (L ), 1,3,5-tris(pyridin-3-ylethynyl)benzene 1 a, 1,3,5-tris[4-(3-pyridyl)phenyl]benzene 2 a, and the hexyloxy chain functionalized derivatives 1,3,5-tris[(3-hexyloxy-5-pyridyl)ethynyl]benzene 1 b, and 1,3,5-tris[4-(3-hexyloxy-5-pyridyl)phenyl]benzene 2 b, were synthesized and used to generate a family of [Pd (L ) ](BF ) octahedral cages (L =1 a, b or 2 a, b). The ligands and cages were characterized using a combination of H, C, and DOSY nuclear magnetic resonance (NMR) spectroscopy, high resolution electrospray mass spectrometry (HR-ESI-MS), infrared (IR) spectroscopy, elemental analysis, and in three cases, X-ray crystallography. The molecular recognition properties of the cages with neutral and anionic guests were examined, in dimethyl sulfoxide (DMSO), using NMR spectroscopy, mass spectrometry and molecular modeling. No binding was observed with simple aliphatic and aromatic guest molecules. However, anionic sulfonates were found to interact with the octahedral cages and the binding interaction was size selective. The smaller [Pd (1 a, b) ] cages were able to interact with three p-toluenesulfonate guest molecules while the larger [Pd (2 a, b) ] systems could host four of the anionic guest molecules. To probe the importance of the hydrophobic effect, a mixed water-DMSO (1:1) solvent system was used to reexamine the binding of the neutral organic guests adamantane, anthracene, pyrene and 1,8-naphthalimide within the cages. In this solvent system all the guests except adamantane were observed to bind within the cavities of the cages. NMR spectroscopy and molecular modeling indicated that the cages bind multiple copies of the individual guests (between 3-6 guest molecules per cage).
