| Autor: |
Fioravanti, Lorenzo, Bellucci, Luca, Armelao, Lidia, Bottaro, Gregorio, Marchetti, Fabio, Pineider, Francesco, Poneti, Giordano, Samaritani, Simona, Labella, Luca |
| Zdroj: |
Inorganic Chemistry; 20210101, Issue: Preprints |
| Abstrakt: |
Mononuclear rare-earth tris-β-diketonato complexes RE(tta)3dme [RE = Y (1), La (2), Dy (3), or Eu (4); Htta = 2-thenoylacetone; dme = 1,2-dimethoxyethane] react cleanly at room temperature in a 1:1 molar ratio with the heteroditopic divergent ligand 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine N-oxide (pyterpyNO) to yield RE2(tta)6(pyterpyNO)n, where n= 2 for RE = Y (5), Dy (6), or Eu (7) and n= 3 for RE = La (8). The crystal structure of 5revealed a dinuclear compound with two pyterpyNO’s bridging through the oxygen atom in a hypodentate mode leaving the terpyridine moieties uncoordinated. Using a metal:pyterpyNO molar ratio of 2 for RE = Y (9), Dy (10), or Eu (11), it was possible to isolate the molecular complexes RE4(tta)12(pyterpyNO)2, while using a 5:3 molar ratio, the product La5(tta)12(pyterpyNO)3(12) can be obtained. 89Y nuclear magnetic resonance spectroscopy revealed two different yttrium centers at room temperature for 9. An X-ray diffraction study of 10showed a symmetrical tetranuclear structure resulting from the coordination of two Dy(tta)3fragments to the two hypodentate terpyridines of the dinuclear unit and presenting two different coordination sites for metals with coordination numbers of 8 and 9. Magnetic studies of 6and 10revealed the presence of an antiferromagnetic interaction between the two Dy(III) atoms bound by the NO bridges. These compounds displayed a slow relaxing magnetization through Orbach (6) and Raman (10) processes in the absence of an applied magnetic field; the rate increased upon application of a 1 kOe field. 7and 11showed a bright red emission typical of Eu3+. The two complexes have similar emission properties mainly determined by the employed β-diketonato ligands. |
| Databáze: |
Supplemental Index |
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