Molecular and Environmental Sciences Group, Department of Geological Sciences, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5E2, Canada.
Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025, United States.
J Phys Chem A. 2023 Apr 27;127(16):3692-3704. doi: 10.1021/acs.jpca.2c08647. Epub 2023 Mar 13.
The sulfones are a widespread group of organo-sulfur compounds, which contain the sulfonyl SO group attached to two carbons and have a formal sulfur oxidation state of +2. We have examined the sulfur K near-edge X-ray absorption spectroscopy (XAS) of a range of different sulfones and find substantial spectroscopic variability depending upon the nature of the coordination to the sulfonyl group. We have also examined the sulfur Kβ X-ray emission spectroscopy (XES) of selected representative sulfones. Density functional theory simulations show satisfactory reproduction of both absorption and emission spectra while enabling assignment of the various transitions comprising the spectra. The correspondence between observed and simulated spectra shows promise for ab initio prediction of sulfur X-ray absorption and emission spectra of sulfones of any substituent. The absorption spectra and, to a lesser extent, the emission spectra are sensitive to the nature of the organic groups bound to the sulfonyl (SO) moiety, clearly showing the potential of X-ray spectroscopy as an in situ probe of sulfone chemistry.
砜是一类广泛存在的有机硫化合物，含有连接两个碳原子的磺酰基 SO 基团，其形式硫氧化态为+2。我们研究了一系列不同砜的硫 K 边近边 X 射线吸收光谱（XAS），发现其光谱具有很大的可变性，这取决于磺酰基的配位性质。我们还研究了选定代表性砜的硫 Kβ X 射线发射光谱（XES）。密度泛函理论模拟能够很好地重现吸收和发射光谱，同时能够对构成光谱的各种跃迁进行分配。观察到的光谱和模拟光谱之间的一致性为预测任何取代基的砜的硫 X 射线吸收和发射光谱提供了有希望的前景。吸收光谱，在较小程度上还有发射光谱，对与磺酰基（SO）部分结合的有机基团的性质敏感，清楚地显示出 X 射线光谱作为砜化学的原位探针的潜力。
