Proton Transfer on the Edge of the Salt/Cocrystal Continuum: X-Ray Photoelectron Spectroscopy of Three Isonicotinamide Salts
Proton Transfer on the Edge of the Salt/Cocrystal Continuum: X-Ray Photoelectron Spectroscopy of Three Isonicotinamide Salts
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DOI：
10.1021/acs.cgd.1c00807
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发表时间：
2021-09-30
影响因子：
3.8
通讯作者：
Schroeder, Sven L. M.
中科院分区：
文献类型：
--
作者：
Edwards, Paul T.;Saunders, Lucy K.;Schroeder, Sven L. M.
X射线光电子能谱(XPS)是一种可以对有机晶体结构中的氢键和质子转移相互作用进行表征和分类的技术，它是对X射线或中子衍射结晶学的补充。在这里，我们分析了异烟酰胺(IN)体系的氮是芯级结合能(BES)，该体系具有短距离的给体和受体之间的质子转移。我们展示了对Be标度的仔细校准如何将这些盐系统正确地置于所谓的盐-共晶体连续体的边缘。我们展示了如何对数据进行与元素分析、预期化学计量比和外来碳污染的量化一致的适配分析，以便于在+/-0.1 eV范围内准确和重现性地确定绝对BES。质子化In受主的N IS核能级BES表明，施主、受主和质子的局域几何排列对N IS核能级BE有显著影响。
X-ray photoelectron spectroscopy (XPS) has emerged as a technique that allows for characterization and classification of hydrogen bonding and proton transfer interactions in organic crystal structures, in a way that is complementary to crystallography by X-ray or neutron diffraction. Here, we analyze the nitrogen is core-level binding energies (BEs) of isonicotinamide (IN) systems with proton transfer between donor and acceptor groups at short distances. We show how a careful calibration of the BE scale places these salt systems correctly on the edge of the so-called salt-cocrystal continuum. We show how performing a fitting analysis of the data that is consistent with elemental analysis, expected stoichiometry, and quantification of adventitious carbon contamination facilitates the determination of absolute BEs with accuracy and reproducibility within +/- 0.1 eV. The determined N is core-level BEs of the protonated IN acceptors suggest that the local geometric arrangements of the donor, acceptor, and proton can influence the N is core-level BE significantly.