X-ray Spectroscopy of Thin Film Free-Base Corroles: A Combined Theoretical and Experimental Characterization
X-ray Spectroscopy of Thin Film Free-Base Corroles: A Combined Theoretical and Experimental Characterization
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DOI：
10.1021/acs.jpcc.6b09935
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发表时间：
2017-02-02
影响因子：
3.7
通讯作者：
Gerstmann, U.
中科院分区：
文献类型：
--
作者：
Aldahhak, H.;Paszkiewicz, M.;Gerstmann, U.
咔咯化合物由于其稳定高价金属态的潜力而吸引了越来越多的兴趣。X射线光谱是研究和开发功能界面的有力工具。然而，对于腐蚀性物种，缺少所需的参考数据。在这里，我们采用了多技术的X射线研究薄膜的原型游离碱5，10，15-三（五氟苯基）咔咯（3 H-TpFPC）生长在Ag（111）表面上的真空条件下。制备了超纯的可咯多层膜样品，并用X射线光电子能谱（XPS）和近边X射线吸收精细结构谱（NEXAFS）对其进行了表征。平行地，X射线指纹模拟使用连续分数的方法在密度泛函理论（DFT）扩展，（准）周期性分子结构。实验和理论光谱之间的一个很好的协议，使详细的光谱特征的透彻的解释，并证明在本DFT方法内的自由基咔咯电子结构的准确描述。本研究提供了X-射线光谱参考的所有相关的核心水平的区域和完整的分子物种的吸收边，因此，代表了一个理想的起点，全面了解的复杂化学的corroles在吸附状态的发展相关的功能接口。
Corrole compounds attract increasing interest due to their potential to stabilize high-valent metal states. Xray spectroscopy is a powerful tool for the investigation and development of functional interfaces. For corrolic species, however, the required reference data are missing. Here, we employ a multitechnique X-ray investigation of thin films of the prototypical free-base 5,10,15-tris(pentafluoropheny1)corrole (3H-TpFPC) grown on the Ag(111) surface under ultrahigh vacuum conditions. Ultrapure corrole multilayer samples are prepared and characterized by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine Structure (NEXAFS) spectroscopy. In parallel, the X-ray fingerprints are simulated using the continued-fraction approach within density functional theory (DFT) for extended, (quasi-)periodic molecular structures. An excellent agreement between experimental and theoretical spectra enables a thorough interpretation of the detailed spectral features and proves an accurate description of the free-base corrole electronic structure within the present DFT approach. The present study provides X-ray spectroscopic references for all relevant core-level regions and absorption edges of intact molecular species and, thus, represents an ideal starting point for the comprehensive understanding of the complex chemistry of corroles in the adsorbed state toward the development of related functional interfaces.