Copper-containing metalloenzymes feature active sites with limited conformational flexibility to enable rapid electron transfer to and from the active site. Here, we present a CuII complex and its CuI analogue with a dpaSMe (dpaSMe = dipicolylaniline) framework capable of facilitating reversible electron transfer and interconverting between trigonal bipyramidal and square pyramidal geometries in solution. These complexes have been structurally characterized by X-Ray diffraction, NMR, EPR, and variable-temperature NMR/EPR spectroscopies and their electronic structure studied by cyclic voltammetry and UV-Visible spectroscopy. The complexes were interrogated by DFT/TD-DFT to further clarify the observed conformational dynamics. The data suggests that both trigonal bipyramidal and square pyramidal complexes of CuII exist simultaneously in solution and that these are capable of interconversion. The implications of this equilibrium on electron transfer chemistry in these systems will be discussed.

Synthesis and characterization of a CuII complex in two geometries

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