Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5375236 | Chemical Physics | 2009 | 11 Pages |
Abstract
The coumarin ligand, 4-hydroxy-3-nitro-2H-chromen-2-one (Hhnc) and its Cu(II) and Ag(I) complexes were studied by DFT calculations at B3LYP/B1 and PW91/B1 levels. MEP of the deprotonated ligand, hncâ, and energy calculations of model metal complexes predicted the ligand binding to the metal ion through the hydroxyl and the nitro oxygens in agreement with experiment. Based on precisely selected Cu/Ag model complexes with hncâ, a relation between the vibrational behaviour of the ligand donor groups and the ligand binding modes in the complexes was deduced. The observed carbonyl ν(CO) downshift (50-90 cmâ1) is attributed to intermolecular H-bonding formed between the CO group and lattice water molecules or due to the CO binding to the metal ion in case of bridging coumarin ligand (in Aghnc). Much larger ν(CO) downshift (â¼220-240 cmâ1) is predicted in case of monodentate or bidentate (with the nitro group) bonding of the carbonyl CO group to the metal ion.
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Authors
Ivelina Georgieva, Natasha Trendafilova, Bernadette S. Creaven, Maureen Walsh, Andy Noble, Malachy McCann,