Effect of Molecular Guest Binding on the d-d Transitions of Ni(2+) of CPO-27-Ni: A Combined UV-Vis, Resonant-Valence-to-Core X-ray Emission Spectroscopy, and Theoretical Study
| Autor: | Francesca Bonino, Sachin Chavan, Gabriele Ricchiardi, Alexander A. Guda, Diego Gianolio, Evgeny Gorelov, Carlo Lamberti, Elisa Borfecchia, Aram L. Bugaev, Erik Gallo |
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| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: |
Analytical chemistry
02 engineering and technology Electronic structure 010402 general chemistry 01 natural sciences MOFS law.invention Inorganic Chemistry METAL-ORGANIC FRAMEWORKS Ultraviolet visible spectroscopy law Emission spectrum Physical and Theoretical Chemistry Spectroscopy HYDROGEN STORAGE GAS-ADSORPTION SITES Valence (chemistry) Chemistry 021001 nanoscience & nanotechnology Synchrotron 0104 chemical sciences Physical chemistry Metal-organic framework Electron configuration 0210 nano-technology |
| Popis: | We used Ni K-edge resonant-valence-to-core X-ray emission spectroscopy (RVtC-XES, also referred to as direct RIXS), an element-selective bulk-sensitive synchrotron-based technique, to investigate the electronic structure of the CPO-27-Ni metal–organic framework (MOF) upon molecular adsorption of significant molecular probes: H2O, CO, H2S, and NO. We compare RVtC-XES with UV–vis spectroscopy, and we show that the element selectivity of RVtC-XES is of strategic significance to observe the full set of d–d excitations in Ni2+, which are partially overshadowed by the low-energy π–π* transitions of the Ni ligands in standard diffuse-reflectance UV–vis experiments. Our combined RVtC-XES/UV–vis approach provides access to the whole set of d–d excitations, allowing us a complete discussion of the changes undergone by the electronic configuration of the Ni2+ sites hosted within the MOF upon molecular adsorption. The experimental data have been interpreted by multiplet ligand-field theory calculations based on Wanni... |
| Databáze: | OpenAIRE |
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