May 18, 2021 Dataset Open Access

Matt Queen; Farideh Jalilehvand; Robert K Szilagyi

Dublin Core Export

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  <dc:creator>Matt Queen</dc:creator>
  <dc:creator>Farideh Jalilehvand</dc:creator>
  <dc:creator>Robert K Szilagyi</dc:creator>
  <dc:date>2021-05-18</dc:date>
  <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.

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

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

DFT_CALCULATIONS
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:identifier>https://zenodo.org/record/4770724</dc:identifier>
  <dc:identifier>10.5281/zenodo.4770724</dc:identifier>
  <dc:identifier>oai:zenodo.org:4770724</dc:identifier>
  <dc:relation>doi:10.5281/zenodo.4770723</dc:relation>
  <dc:rights>info:eu-repo/semantics/openAccess</dc:rights>
  <dc:rights>https://creativecommons.org/licenses/by/4.0/legalcode</dc:rights>
  <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>
  <dc:type>info:eu-repo/semantics/other</dc:type>
  <dc:type>dataset</dc:type>
</oai_dc:dc>