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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

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->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.

manuscript submitted for publication
Files (101.8 MB)
Name Size
__README.txt
md5:40ddd90b77fb081af78563bfd2a27c7d
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DFT_CALCULATIONS.zip
md5:1626b72a0039782c6f0055adb9829b5d
92.0 MB Download
RAW_DATA.zip
md5:f26e3e11b62b20930bdd67739a261c4f
339.9 kB Download
spectral modeling summary.xlsx
md5:9019c6d4c6da246ea0c6a53f536b0550
5.5 MB Download
SPECTRAL_MODELS.zip
md5:315da1c5ff66bd410e8f6f6b4bd4289e
2.7 MB Download
transition dipole.xls
md5:81a8981495d21b890700b42a74e63a2c
1.1 MB Download
XRD_STRUCTURES.zip
md5:3cf2a8c64c89662a0956540b7c59ca54
235.4 kB Download
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