MURAL - Maynooth University Research Archive Library



    Is the C=O frequency shift a reliable indicator of coumarin binding to metal ions through the carbonyl oxygen?


    Georgieva, Ivelina and Trendafilova, Natasha and Creaven, Bernadette S. and Walsh, Maureen and Noble, Andy and McCann, Malachy (2009) Is the C=O frequency shift a reliable indicator of coumarin binding to metal ions through the carbonyl oxygen? Chemical Physics, 365. pp. 69-79.

    [img]
    Preview
    Download (1MB) | Preview
    Official URL: https://www.journals.elsevier.com/chemical-physics


    Share your research

    Twitter Facebook LinkedIn GooglePlus Email more...



    Add this article to your Mendeley library


    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, hnc-, 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 hnc-, a relation between the vibrational behaviour of the ligand donor groups and the ligand binding modes in the complexes was deduced. The observed carbonyl m(C=O) downshift (50–90 cm-1) is attributed to intermolecular H-bonding formed between the C@O group and lattice water molecules or due to the C@O binding to the metal ion in case of bridging coumarin ligand (in Aghnc). Much larger m(C=O) downshift (~220–240 cm-1) is predicted in case of monodentate or bidentate (with the nitro group) bonding of the carbonyl C=O group to the metal ion.

    Item Type: Article
    Keywords: Ag(I); Cu(II) complexes; Coumarin; DFT modeling; Electronic structure; IR spectra;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Item ID: 9676
    Depositing User: Dr. Malachy McCann
    Date Deposited: 13 Jul 2018 11:40
    Journal or Publication Title: Chemical Physics
    Publisher: Elsevier
    Refereed: Yes
    URI:

      Repository Staff Only(login required)

      View Item Item control page

      Downloads

      Downloads per month over past year