Optical properties of Eu(III) and Tb(III) complexes with pyridine- and quinoline- based ligands under high hydrostatic pressure
| Autor: | Chiara De Rosa, Marek Grinberg, Fabio Piccinelli, Marco Bettinelli, Takayuki Nakanishi, Shun Omagari, Agata Lazarowska, Sebastian Mahlik |
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| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Metal ions in aqueous solution
Imine Hydrostatic pressure 010402 general chemistry 01 natural sciences Coordination complex Inorganic Chemistry chemistry.chemical_compound Luminescence spectroscopy DPT calculations Pyridine Materials Chemistry Molecular orbital Physical and Theoretical Chemistry chemistry.chemical_classification 010405 organic chemistry Quinoline Coordination chemistry Molecular orbitals Lanthanide ions 0104 chemical sciences Crystallography chemistry Excited state |
| Popis: | The spectroscopy of nitrate complexes of Eu(III) and Tb(III) with chiral and racemic imine-based [L1 = (N,N’-bis(2-pyridylmethylidene)-1,2-(R,R + S,S)-cyclohexanediamine) and L3 = N, N’-bis(2-quinolylmethylidene)-1,2-(R,R + S,S)-cyclohexanediamine] and amine-based [L2 = N,N’-bis(2-pyridylmethyl)-1,2-(R,R + S,S)-cyclohexanediamine) and L4 = N,N’-bis(2-quinolylmethyl)-1,2-(R,R + S,S)-cyclohexanediamine] ligands has been studied under high hydrostatic pressure (above 100 kbar). With the increasing pressure, a reduction of the Tb(III) and Eu(III) luminescence intensity is detected for all the complexes, whilst a significant reduction of the Tb(III) and Eu(III) excited state lifetimes has been observed for all Tb-based complexes [L1Tb(NO3)3 → L4Tb(NO3)3] and only for the Eu(III) complexes containing the imine-based ligands [L1Eu(NO3)3 and L3Eu(NO3)3]. This behavior has been rationalized taking into account two main aspects: i) the relative position of the energy levels of the ligands and the metal ions and ii) the change of these position upon compression DFT calculations have been also performed to elucidate the nature of the orbitals involved in the UV electronic absorption transitions (NTO orbitals) upstream of the energy transfer process to the metal ion. |
| Databáze: | OpenAIRE |
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