Add time:08/12/2019         Source:sciencedirect.com

New monometallic bis-bipyridyl Ru(II) and Os(II) complexes bonded with high nitrogen content five membered aromatic dianionic ligands 5,5′-bis-tetrazolate (bt) and N,N-bis(tetrazol-5-yl)-amine (bta) have been prepared. NMR results presented are consistent with N1-N1 bidentate chelate bonding to the metal. Absorption spectra display lower energy M dπ → bpy π∗ metal to ligand charge transfer transitions than the respective tris bipyridyl complexes, and the results are consistent with the π donating ability of the bt and bta dianions. Density function theory calculations for all complexes show the HOMO are predominately M dπ-bt π and M dπ-bta π character while the LUMO are M dπ-bpy π∗ character. The M+2/+3 oxidation potentials are less positive, and bpy0/−1 reduction potentials are at more negative potentials than the respective tris bipyridyl complexes, which is consistent with increased electron donation from the bt and bta dianionic ligands to the metal.

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