May 18, 2021 Dataset Open Access

Matt Queen; Farideh Jalilehvand; Robert K Szilagyi

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    <subfield code="u">Montana State University - Billings</subfield>
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    <subfield code="a">&lt;p&gt;&lt;em&gt;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)&lt;sub&gt;4&lt;/sub&gt;]&lt;sup&gt;2+&lt;/sup&gt;, [Co(TU)&lt;sub&gt;4&lt;/sub&gt;]&lt;sup&gt;2+&lt;/sup&gt;, and [Ni(TU)&lt;sub&gt;6&lt;/sub&gt;]&lt;sup&gt;2+&lt;/sup&gt; complexes.&lt;/em&gt;&lt;/p&gt;

&lt;blockquote&gt;
&lt;p&gt;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&lt;sup&gt;2+&lt;/sup&gt;, Co&lt;sup&gt;2+&lt;/sup&gt;, and Ni&lt;sup&gt;2+ &lt;/sup&gt;ions in distorted tetrahedral and octahedral homoleptic coordination environments. Comparisons of XAS spectra of the free TU ligand, [Zn(TU)&lt;sub&gt;4&lt;/sub&gt;]&lt;sup&gt;2+&lt;/sup&gt;, [Co(TU)&lt;sub&gt;4&lt;/sub&gt;]&lt;sup&gt;2+&lt;/sup&gt;, and [Ni(TU)&lt;sub&gt;6&lt;/sub&gt;]&lt;sup&gt;2+&lt;/sup&gt; complexes clearly identify spectral features emerging from the structural non-innocent TM&lt;sup&gt;2+&lt;/sup&gt;&amp;ndash;S(TU) bonding. Quantitative analysis of pre-edge intensities describes the covalency of Ni&lt;sup&gt;2+&lt;/sup&gt;&amp;ndash; and Co&lt;sup&gt;2+&lt;/sup&gt;&amp;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&lt;sup&gt;2+&lt;/sup&gt; complexes with dithiocarbamate and thioether ligands, we evaluated the empirical S 1s&amp;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.&lt;/p&gt;
&lt;/blockquote&gt;

&lt;p&gt;&lt;em&gt;Table of Contents:&lt;/em&gt;&lt;/p&gt;

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

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

&lt;p&gt;&lt;strong&gt;SPECTRAL_MODELS folder&lt;/strong&gt;&lt;br&gt;
Electronic spreadsheets, PeakFit spectral fitting templates, spectra as user-defined functions, quantitative analysis of pre-edge feature intensities&lt;/p&gt;

&lt;p&gt;&lt;strong&gt;XRD_STRUCTURES folder&lt;/strong&gt;&lt;br&gt;
Xmol (XYZ) and DSViewerPro (MSV) files for the analysis of the crystal packing environment of TU complexes.&lt;/p&gt;

&lt;p&gt;&lt;strong&gt;DFT_CALCULATIONS&lt;/strong&gt;&lt;br&gt;
Gaussian09 log files for free thiourea, Co&lt;sup&gt;(II)&lt;/sup&gt; and Ni&lt;sup&gt;(II)&lt;/sup&gt; complexes at BP86/def2TZVP, B3LYP/def2TZVP, and TPSS/def2TZVP levels of theory; frequency calculations for IR vibrational spectral simulations.&lt;/p&gt;</subfield>
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