Site-specific electronic structure of covalently linked bimetallic dyads from nitrogen K-edge x-ray absorption...

A nitrogen K-edge x-ray absorption near-edge structure (XANES) survey is presented for tetrapyrido[3,2-a:2',3'-c:3″,2″-h:2‴,3‴-j]phenazine (tpphz)-bridged bimetallic assemblies that couple chromophore and catalyst transition metal complexes for light driven catalysis, as well as their individual molecular constituents. We demonstrate the high N site sensitivity of the N pre-edge XANES features, which are energetically well-separated for the phenazine bridge N atoms and for the individual metal-bound N atoms of the inner coordination sphere ligands. By comparison with the time-dependent density functional theory calculated spectra, we determine the origins of these distinguishable spectral features. We find that metal coordination generates large shifts toward higher energy for the metal-bound N atoms, with increasing shift for 3d < 4d < 5d metal bonding. This is attributed to increasing ligand-to-metal σ donation that increases the effective charge of the bound N atoms and stabilizes the N 1s core electrons. In contrast, the phenazine bridge N pre-edge peak is found at a lower energy due to stabilization of the low energy electron accepting orbital localized on the phenazine motif. While no sensitivity to ground state electronic coupling between the individual molecular subunits was observed, the spectra are sensitive to structural distortions of the tpphz bridge. These results demonstrate N K-edge XANES as a local probe of electronic structure in large bridging ligand motifs, able to distinctly investigate the ligand-centered orbitals involved in metal-to-ligand and ligand-to-ligand electron transfer following light absorption.