Spectroscopic and Electrochemical Trends in Divalent Lanthanides through Modulation of Coordination Environment.

Due to the importance of both visible-light luminescence and lanthanides in modern society, the influence of the ligand environment on complexes of YbII were studied and compared with analogous complexes of EuII. Four ligands with systematically varied electronic and steric characteristics were used to probe the coordination environment and electronic and redox properties of the corresponding YbII-containing complexes. Strong-field nitrogenous donors gave rise to bathochromic shifts, leading to visible-light absorption by YbII. Trends in properties across the series of YbII-containing complexes were compared to trends reported for the analogous EuII-containing complexes, revealing the translatability of coordination environment effects across the divalent lanthanide series. These studies provide valuable information regarding the behavior of small and medium-sized divalent lanthanides outside of the solid state.

Solid-state and solution-phase characterization of SmII-aza[2.2.2]cryptate and its methylated analogue.

Two new SmII-azacryptates are reported that differ in steric hindrance and Lewis basicity of donor atoms. The sterically hindered complex has a smaller coordination number and a more negative electrochemical potential than the complex with less steric hindrance.

First use of a divalent lanthanide for visible-light-promoted photoredox catalysis.

We report the first catalytic use of a divalent lanthanide in visible-light-promoted bond-forming reactions. Our new precatalyst uses europium in the +2 oxidation state and is active in the presence of blue light from light-emitting diodes. The use of low-energy visible light reduces the occurrence of potential side reactions that might be induced by higher-energy UV light. The system described here uses zinc metal as a sacrificial reductant and is tolerant to wet, protic solvents. The catalyst can be made in situ from relatively inexpensive and air-stable EuCl3·6H2O, and the ligand can be synthesized in large quantities in two steps. With 0.5% loading of precatalyst, an average of 120 turnovers was observed in six hours for reductive coupling of benzyl chloride. We expect that the results will initiate the study of visible-light-promoted photoredox catalysis using divalent europium in a variety of reactions.

Photophysical characterization of a highly luminescent divalent-europium-containing azacryptate.

We report a new luminescent EuII-containing complex. The complex is excited with visible light, leading to emission centered at 447 nm with a lifetime of 1.25 µs. Computational studies suggest that the steric bulk of the ligand is a major factor influencing the wavelength of emission.