Ligand Effects on the Emission Characteristics of Molecular Eu(II) Luminescence Thermometers

Discrete molecular organometallic europium(II) complexes are promising functional materials due to their ability to behave as highly sensitive band-shift luminescence thermometers. Furthering our understanding of the design principles salient to the emission behavior of such systems is important for developing them in this emerging application. To this end, a series of pseudo-C_4v-symmetric organometallic europium(II) complexes bearing systematically varying ligand sets were synthesized and characterized to probe the influence of subtle structural modification on their optical properties. Opto-structural correlation analyses via variable-temperature single-crystal X-ray diffraction and photoluminescence spectroscopy reveal a remarkable variability in properties among structurally similar complexes and a convoluted dependence of the emission characteristics on the stereoelectronic properties of the ligands. A few factors of particular influence are nevertheless identified, including the distance between the europium(II) ion and the basal plane of the square-pyramidal coordination polyhedron, the presence of pendant electron density that might further interact with the excited-state 5d orbitals, and, qualitatively, the metal-ligand flexibility of the construct. These results help to elucidate principles that govern the luminescence properties of organometallic europium(II) complexes with an eye to enabling the rational design of high-performance luminescence thermometers of this genre.