May 18, 2021 Dataset Open Access

Matt Queen; Farideh Jalilehvand; Robert K Szilagyi

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{
  "description": "<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>", 
  "license": "https://creativecommons.org/licenses/by/4.0/legalcode", 
  "creator": [
    {
      "affiliation": "Montana State University - Billings", 
      "@type": "Person", 
      "name": "Matt Queen"
    }, 
    {
      "affiliation": "University of Calgary", 
      "@type": "Person", 
      "name": "Farideh Jalilehvand"
    }, 
    {
      "affiliation": "Montana State University", 
      "@id": "https://orcid.org/0000-0002-9314-6222", 
      "@type": "Person", 
      "name": "Robert K Szilagyi"
    }
  ], 
  "url": "https://zenodo.org/record/4770724", 
  "datePublished": "2021-05-18", 
  "keywords": [
    "sulfur K-edge XANES", 
    "thiourea complexes", 
    "non-innocent S-ligand", 
    "transition dipole integral", 
    "metal-ligand bond covalency", 
    "ground electronic state", 
    "molecular orbital composition"
  ], 
  "version": "1.0", 
  "contributor": [], 
  "@context": "https://schema.org/", 
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  "identifier": "https://doi.org/10.5281/zenodo.4770724", 
  "@id": "https://doi.org/10.5281/zenodo.4770724", 
  "@type": "Dataset", 
  "name": "Sulfur K-edge X-ray absorption near-edge spectral analysis of thiourea free ligand and its Zn(II), Co(II), and Ni(II) complexes"
}