Dataset Open Access
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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<dct: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</dct:title>
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<dct:issued rdf:datatype="http://www.w3.org/2001/XMLSchema#gYear">2021</dct:issued>
<dcat:keyword>sulfur K-edge XANES</dcat:keyword>
<dcat:keyword>thiourea complexes</dcat:keyword>
<dcat:keyword>non-innocent S-ligand</dcat:keyword>
<dcat:keyword>transition dipole integral</dcat:keyword>
<dcat:keyword>metal-ligand bond covalency</dcat:keyword>
<dcat:keyword>ground electronic state</dcat:keyword>
<dcat:keyword>molecular orbital composition</dcat:keyword>
<dct:issued rdf:datatype="http://www.w3.org/2001/XMLSchema#date">2021-05-18</dct:issued>
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<dct: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> <blockquote> <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> </blockquote> <p><em>Table of Contents:</em></p> <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> <p><strong>RAW_DATA folder:</strong><br> ASCII 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> <p><strong>SPECTRAL_MODELS folder</strong><br> Electronic spreadsheets, PeakFit spectral fitting templates, spectra as user-defined functions, quantitative analysis of pre-edge feature intensities</p> <p><strong>XRD_STRUCTURES folder</strong><br> Xmol (XYZ) and DSViewerPro (MSV) files for the analysis of the crystal packing environment of TU complexes.</p> <p><strong>DFT_CALCULATIONS</strong><br> Gaussian09 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></dct:description>
<dct:description>manuscript submitted for publication</dct:description>
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Indexed in
- Publication date:
- May 18, 2021
- DOI:
-
- Keyword(s):
- sulfur K-edge XANES thiourea complexes non-innocent S-ligand transition dipole integral metal-ligand bond covalency ground electronic state molecular orbital composition
- License (for files):
- Creative Commons Attribution 4.0 International