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.

The Influence of Secondary Interactions on the [N-I-N] Halogen Bond.

[Bis(pyridine)iodine(I)] complexes offer controlled access to halonium ions under mild conditions. The reactivity of such stabilized halonium ions is primarily determined by their three-center, four-electron [N-I-N] halogen bond. We studied the importance of chelation, strain, steric hindrance and electrostatic interaction for the structure and reactivity of halogen bonded halonium ions by acquiring their N NMR coordination shifts and measuring their iodenium release rates, and interpreted the data with the support of DFT computations.