期刊
INORGANIC CHEMISTRY
卷 55, 期 21, 页码 11497-11501出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.6b02053
关键词
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资金
- Max Planck Society
- Canadian Light Source [21-6672, 21-7280]
Spectroscopic probes of the electronic structure of transition metal-containing materials are invaluable to the design of new molecular catalysts and magnetic systems. Herein, we show that 2p3d resonant inelastic X-ray scattering (RIXS) can be used to observe both spin-allowed and (in the V-III case) spin-forbidden d-d excitation energies in molecular vanadium complexes. The spin-allowed d-d excitation energies determined by 2p3d RIXS are in good agreement with available optical data. In V(acac)(3), a previously undetected spin-forbidden singlet state has been observed. The presence of this feature provides a ligand-field independent signature of V-III. It is also shown that d-d excitations may be obtained for porphyrin complexes. This is generally prohibitive using optical approaches due to intense porphyrin pi-to-pi* transitions. In addition, the intensities of charge transfer features in 2p3d RIXS spectroscopy are shown to be a clear indication of metal-ligand covalency. The utility of 2p3d RIXS for future studies of complex inorganic systems is highlighted.
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