Combining Topological and Steric Constraints for the Preparation of Heteroleptic Copper(I) Complexes

Heteroleptic copper(I) complexes have been prepared from a macrocyclic ligand incorporating a 2,9-diphenyl- 1,10-phenanthroline subunit (M30) and two bis-phosphines, namely bis[(2-diphenylphosphino) phenyl] ether (POP) and 1,3-bis(diphenylphosphino) propane (dppp). In both cases, the diphenylphosphino moieties of the PP ligand are too bulky to pass through the 30-membered ring of M30 during the coordination process, hence the formation of C-2v-symmetrical pseudo-rotaxanes is prevented. When POP is used, X-ray crystal structure analysis shows the formation of a highly distorted [Cu(M30)(POP)](+) complex in which the POP ligand is only partially threaded through the M30 unit. This compound is poorly stable as the CuI cation is not in a favorable coordination environment due to steric constraints. By contrast, in the case of dppp, the bis-phosphine ligand undergoes both steric and topological constraints and adopts a nonchelating coordination mode to generate [Cu2(M30) 2(m-dppp)](BF4)(2). This compound exhibits metal-to-ligand charge transfer (MLCT) emission characterized by a very large Stokes' shift (similar to 200 nm) that is not attributed to a dramatic structural distortion between the ground and the emitting states but to very weak MLCT absorption transitions at longer wavelengths. Accordingly, [Cu-2(M30)(2)(mu-dppp)](BF4)(2) shows unusually high luminescence quantum yields for CuI complexes, both in solution and in the solid state (0.5 and 7%, respectively).