Levin Natalia, Peredkov Sergey, Weyhermüller Thomas, Rüdiger Olaf, Pereira Nilson B, Grötzsch Daniel, Kalinko Aleksandr, DeBeer Serena
Max Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, 45470 Mülheim an der Ruhr, Germany.
Institut für Optik und Atomare Physik (IOAP), TU-Berlin, Hardenbergstr. 36, 10623 Berlin, Germany.
Inorg Chem. 2020 Jun 15;59(12):8272-8283. doi: 10.1021/acs.inorgchem.0c00663. Epub 2020 May 11.
Ruthenium 4d-to-2p X-ray emission spectroscopy (XES) was systematically explored for a series of Ru and Ru species. Complementary density functional theory calculations were utilized to allow for a detailed assignment of the experimental spectra. The studied complexes have a range of different coordination spheres, which allows the influence of the ligand donor/acceptor properties on the spectra to be assessed. Similarly, the contributions of the site symmetry and the oxidation state of the metal were analyzed. Because the 4d-to-2p emission lines are dipole-allowed, the spectral features are intense. Furthermore, in contrast with K- or L-edge X-ray absorption of 4d transition metals, which probe the unoccupied levels, the observed 4p-to-2p XES arises from electrons in filled-ligand- and filled-metal-based orbitals, thus providing simultaneous access to the ligand and metal contributions to bonding. As such, 4d-to-2p XES should be a promising tool for the study of a wide range of 4d transition-metal compounds.
针对一系列钌及钌物种，系统地研究了钌的4d到2p X射线发射光谱（XES）。利用互补的密度泛函理论计算对实验光谱进行详细归属。所研究的配合物具有一系列不同的配位球，这使得能够评估配体供体/受体性质对光谱的影响。同样，分析了位点对称性和金属氧化态的贡献。由于4d到2p发射线是偶极允许的，光谱特征很强。此外，与探测未占据能级的4d过渡金属的K边或L边X射线吸收不同，观察到的4p到2p XES源于填充配体和填充金属基轨道中的电子，从而能够同时获取配体和金属对成键的贡献。因此，4d到2p XES应该是研究多种4d过渡金属化合物的一种有前景的工具。
