Rapid Access to Encapsulated Molecular Rotors via Coordination-Driven Macrocycle Formation.

Macrocycle formation that relies upon trans metal coordination of appropriately placed pyridine ligands within an arylene ethynylene construct provides rapid and reliable access to molecular rotators encapsulated within macrocyclic stators. Showing no significant close contacts to the central rotators, X-ray crystallography of Ag -coordinated macrocycles provides plausibility for unobstructed rotation or wobbling of rotators within the central cavity. Solid-state C NMR of Pd -coordinated macrocycles supports the notion of unobstructed movement of simple arenes in the crystal lattice.

Effects of Halogen and Hydrogen Bonding on the Electronics of a Conjugated Rotor.

The electronic properties of a pyrazine-containing arylene ethynylene unit are influenced by hydrogen bond and halogen bond donors that are held in proximity of the pyrazine rotor. These interactions are evident with iodine- and bromine-centered halogen bonds and O-H- and C-H-based hydrogen bonds. Bathochromic shifts of UV-vis and fluorescence signals are the best indicators of this intramolecular attraction.