Dinuclear Rhenium Complexes with a Bridging Helicene-bis-bipyridine Ligand: Synthesis, Structure, and Photophysical and Chiroptical Properties

By attaching pyridine groups to a diaza[6]helicene, a helical, bis-ditopic, bis-N N-coordinating ligand can be accessed. Dinuclear rhenium complexes featuring this bridging ligand, of the form [{Re(CO)₃Cl}₂(N N−N N)], have been prepared and resolved to give enantiopure complexes. These complexes are phosphorescent in solution at room temperature under one- and two-photon excitation. Their experimental chiroptical properties (optical rotation, electronic circular dichroism and circularly polarized emission) have been measured. They show, for instance, emission dissymmetry factors of c.a. ±3x10⁻³. Quantum-chemical calculations indicate the importance of stereochemistry on the optical activity, pointing towards further design improvements in such types of complexes.