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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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  "publisher": "Zenodo", 
  "DOI": "10.5281/zenodo.4770724", 
  "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", 
  "issued": {
    "date-parts": [
  "abstract": "<p><em>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)<sub>4</sub>]<sup>2+</sup>, [Co(TU)<sub>4</sub>]<sup>2+</sup>, and [Ni(TU)<sub>6</sub>]<sup>2+</sup> complexes.</em></p>\n\n<blockquote>\n<p>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 Zn<sup>2+</sup>, Co<sup>2+</sup>, and Ni<sup>2+ </sup>ions in distorted tetrahedral and octahedral homoleptic coordination environments. Comparisons of XAS spectra of the free TU ligand, [Zn(TU)<sub>4</sub>]<sup>2+</sup>, [Co(TU)<sub>4</sub>]<sup>2+</sup>, and [Ni(TU)<sub>6</sub>]<sup>2+</sup> complexes clearly identify spectral features emerging from the structural non-innocent TM<sup>2+</sup>&ndash;S(TU) bonding. Quantitative analysis of pre-edge intensities describes the covalency of Ni<sup>2+</sup>&ndash; and Co<sup>2+</sup>&ndash;S(TU) bonding to be at most 23% and 9% as expressed by the S 3p contributions per 3d electron hole. Using relevant Ni<sup>2+</sup> complexes with dithiocarbamate and thioether ligands, we evaluated the empirical S 1s&rarr;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.</p>\n</blockquote>\n\n<p><em>Table of Contents:</em></p>\n\n<p>Worksheets &quot;transition dipole&quot; and &quot;spectral modeling summary&quot; contain data for empirical S 1s-&gt;3p transition dipole integral estimates and summary of spectral modeling, respectively.</p>\n\n<p><strong>RAW_DATA folder:</strong><br>\nASCII formatted S K-edge XAS data from BL 4-3 of SSRL, and data obtained for the [Ni(TU)<sub>6</sub>]<sup>2+</sup> complex at the double-crystal monochromator beamline (formerly Canadian Beamline) of Synchrotron Research Center (the home of Aladdin), in Stoughton, Wisconsin.</p>\n\n<p><strong>SPECTRAL_MODELS folder</strong><br>\nElectronic spreadsheets, PeakFit spectral fitting templates, spectra as user-defined functions, quantitative analysis of pre-edge feature intensities</p>\n\n<p><strong>XRD_STRUCTURES folder</strong><br>\nXmol (XYZ) and DSViewerPro (MSV) files for the analysis of the crystal packing environment of TU complexes.</p>\n\n<p><strong>DFT_CALCULATIONS</strong><br>\nGaussian09 log files for free thiourea, Co<sup>(II)</sup> and Ni<sup>(II)</sup> complexes at BP86/def2TZVP, B3LYP/def2TZVP, and TPSS/def2TZVP levels of theory; frequency calculations for IR vibrational spectral simulations.</p>", 
  "author": [
      "family": "Matt Queen"
      "family": "Farideh Jalilehvand"
      "family": "Robert K Szilagyi"
  "note": "manuscript submitted for publication", 
  "version": "1.0", 
  "type": "dataset", 
  "id": "4770724"
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