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Sulfur K-edge X-ray absorption near-edge spectral analysis of thiourea free ligand and its Zn(II), Co(II), and Ni(II) complexes

Matt Queen; Farideh Jalilehvand; Robert K Szilagyi

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<oai_dc:dc xmlns:dc="" xmlns:oai_dc="" xmlns:xsi="" xsi:schemaLocation="">
  <dc:creator>Matt Queen</dc:creator>
  <dc:creator>Farideh Jalilehvand</dc:creator>
  <dc:creator>Robert K Szilagyi</dc:creator>
  <dc:description>Electronic supporting information for the analysis and interpretation of sulfur K-edge X-ray absorption near-edge spectra of thiourea free ligand and its [Zn(TU)4]2+, [Co(TU)4]2+, and [Ni(TU)6]2+ complexes.

Sulfur K-edge X-ray absorption spectroscopy (XAS) was employed to experimentally define the nature of coordinative bond between thiourea (TU) or thiocarbamide ligand and Zn2+, Co2+, and Ni2+ ions in distorted tetrahedral and octahedral homoleptic coordination environments. Comparisons of XAS spectra of the free TU ligand, [Zn(TU)4]2+, [Co(TU)4]2+, and [Ni(TU)6]2+ complexes clearly identify spectral features emerging from the structural non-innocent TM2+–S(TU) bonding. Quantitative analysis of pre-edge intensities describes the covalency of Ni2+– and Co2+–S(TU) bonding to be at most 23% and 9% as expressed by the S 3p contributions per 3d electron hole. Using relevant Ni2+ complexes with dithiocarbamate and thioether ligands, we evaluated the empirical S 1s→3p transition dipole integrals developed for sulfur ligands and its dependence on heteroatom substitutions. With the aid of density functional theory-based ground electronic state calculations, we found evidence for the need of using a transition dipole that is dependent on the presence of conjugated heteroatom (N) substitution in the S-ligands.

Table of Contents:

Worksheets "transition dipole" and "spectral modeling summary" contain data for empirical S 1s-&gt;3p transition dipole integral estimates and summary of spectral modeling, respectively.

RAW_DATA folder:
ASCII formatted S K-edge XAS data from BL 4-3 of SSRL, and data obtained for the [Ni(TU)6]2+ complex at the double-crystal monochromator beamline (formerly Canadian Beamline) of Synchrotron Research Center (the home of Aladdin), in Stoughton, Wisconsin.

Electronic spreadsheets, PeakFit spectral fitting templates, spectra as user-defined functions, quantitative analysis of pre-edge feature intensities

Xmol (XYZ) and DSViewerPro (MSV) files for the analysis of the crystal packing environment of TU complexes.

Gaussian09 log files for free thiourea, Co(II) and Ni(II) complexes at BP86/def2TZVP, B3LYP/def2TZVP, and TPSS/def2TZVP levels of theory; frequency calculations for IR vibrational spectral simulations.</dc:description>
  <dc:description>manuscript submitted for publication</dc:description>
  <dc:subject>sulfur K-edge XANES</dc:subject>
  <dc:subject>thiourea complexes</dc:subject>
  <dc:subject>non-innocent S-ligand</dc:subject>
  <dc:subject>transition dipole integral</dc:subject>
  <dc:subject>metal-ligand bond covalency</dc:subject>
  <dc:subject>ground electronic state</dc:subject>
  <dc:subject>molecular orbital composition</dc:subject>
  <dc:title>Sulfur K-edge X-ray absorption near-edge spectral analysis of thiourea free ligand and its Zn(II), Co(II), and Ni(II) complexes</dc:title>
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