The quenching of sensitized Eu­(III) luminescence by photoinduced electron transfer from the excited light-harvesting antenna to Eu­(III) was investigated. A series of complexes incorporating different metal binding sites and thus having varying Eu­(III)/Eu­(II) reduction potentials were prepared. The complexes were fully characterized using a combination of single-crystal X-ray crystallography and paramagnetic 1H NMR spectroscopy, the results of which support the structural similarity of the complexes. The redox and photophysical behavior of the Eu­(III) center and the light-harvesting antenna were studied using cyclic voltammetry and steady-state and time-resolved emission spectroscopy on the nanosecond and millisecond time scales. The contribution of photoinduced electron transfer to the overall reduction of the Eu­(III) luminescence quantum yield was found to be comparable and, in many cases, larger than the quenching caused by well-established processes such as coupling to X–H oscillators. These results suggest that the elimination or mitigation of photoinduced electron transfer could substantially improve the emissive properties of the widely used Eu­(III)-based emitters.

A series of luminescent lanthanide(iii) complexes consisting of 1,4,7-triazacyclononane-1,4-picolinate frameworks and three secondary amidelinked carbostyril antennae were synthesised and characterised.

The UIV–RhI intermetallic distances in the U2Rh2 complex (left, 2.7601(5) Å) and URh complex (right, 2.7630(5) Å) are very short and almost identical in the solid state even though solution electrochemistry suggests very different metal-based reduction processes.