Luminescent Complexes of Europium (III) with 2-(Phenylethynyl)-1,10-phenanthroline: The Role of the Counterions.

New antenna ligand, 2-(phenylethynyl)-1,10-phenanthroline (PEP), and its luminescent Eu (III) complexes, Eu(PEP)Cl and Eu(PEP)(NO), are synthesized and characterized. The synthetic procedure applied is based on reacting of europium salts with ligand in hot acetonitrile solutions in molar ratio 1 to 2. The structure of the complexes is refined by X-ray diffraction based on the single crystals obtained. The compounds [Eu(PEP)Cl]·2CHCN and [Eu(PEP)(NO)]∙2CHCN crystalize in monoclinic space group P2 and P2, respectively, with two acetonitrile solvent molecules. Intra- and inter-ligand π-π stacking interactions are present in solid stat and are realized between the phenanthroline moieties, as well as between the substituents and the phenanthroline units. The optical properties of the complexes are investigated in solid state, acetonitrile and dichloromethane solution. Both compounds exhibit bright red luminescence caused by the organic ligand acting as antenna for sensitization of Eu (III) emission. The newly designed complexes differ in counter ions in the inner coordination sphere, which allows exploring their influence on the stability, molecular and supramolecular structure, fluorescent properties and symmetry of the Eu (III) ion. In addition, molecular simulations are performed in order to explain the observed experimental behavior of the complexes. The discovered structure-properties relationships give insight on the role of the counter ions in the molecular design of new Eu (III) based luminescent materials.