Influence of Metal Identity in Bipyridine-Based Metal-4N Complexes With Formate.

We present the vibrational spectra of a series of dicationic, organometallic complexes consisting of a transition metal center (Co, Ni, or Cu) coordinated by 4,4'-di(-butyl)-2,2'-bipyridine (DTBbpy) ligands and a formate adduct. Spectral features are analyzed and assigned through comparison with density functional theory calculations, and structures are reported. Natural population analysis shows that the DTBbpy ligands serve as flexible charge reservoirs in each complex.

Effects of Formate Binding to a Bipyridine-Based Cobalt-4N Complex.

We report the vibrational spectrum of a metal-organic complex consisting of a Co center surrounded by two bipyridine-based ligands and explore the change of the spectrum upon addition of a formate ligand to the complex. We assign the spectra using density functional theory. The infrared response encodes the binding motif of the formate to the metal, and the calculated charge distributions highlight the ability of the organic ligand framework to act as charge reservoirs modulating the redox properties of the metal center.