Use of Crown Ether Functions as Secondary Coordination Spheres for the Manipulation of Ligand-Metal Intramolecular Electron Transfer in Copper-Guanidine Complexes.

Intramolecular electron transfer (IET) between a redox-active organic ligand and a metal in a complex is of fundamental interest and used in a variety of applications. In this work it is demonstrated that secondary coordination sphere motifs can be applied to trigger a radical change in the electronic structure of copper complexes with a redox-active guanidine ligand through ligand-metal IET. Hence, crown ether functions attached to the ligand allow the manipulation of the degree of IET between the guanidine ligand and the copper atom through metal encapsulation.