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Improved Photostability of a CuI Complex by Macrocyclization of the Phenanthroline Ligands
Journal
Chemistry - A European Journal
Volume
26
Number
14
Pages / Article-Number
3119-3128
Abstract
The development of molecular materials for conversion of solar energy into electricity and fuels is one of the most active research areas, in which the light absorber plays a key role. While copper(I)-bis(diimine) complexes [Cu-I(L)(2)](+) are considered as potent substitutes for [Ru-II(bpy)(3)](2+), they exhibit limited structural integrity as ligand loss by substitution can occur. In this article, we present a new concept to stabilize copper bis(phenanthroline) complexes by macrocyclization of the ligands which are preorganized around the Cu-I ion. Using oxidative Hay acetylene homocoupling conditions, several Cu-I complexes with varying bridge length were prepared and analyzed. Absorption and emission properties are assessed; rewardingly, the envisioned approach was successful since the flexible 1,4-butadiyl-bridged complex does show enhanced MLCT absorption and emission, as well as improved photostability upon irradiation with a blue LED compared to a reference complex.
