Macrocycle supported dinuclear lanthanide complexes with different β-diketonate co-ligands displaying zero field single-molecule magnetic behaviour
Three different sets of isomorphous dinuclear Gd/Dy complexes, [Ln 2 (L′)(acac) 4 ]·2H 2 O·2CH 3 CN (Ln = Gd ( 1 Gd ) and Dy ( 2 Dy ); acac = acetylacetonate), [Ln 2 (L′)(tfac) 4 ] (Ln = Gd ( 3 Gd ) and Dy ( 4 Dy ); tfac = trifluoroacetylacetonate), and [Ln 2 (L′)(hfac) 4 ] (Ln = Gd ( 5 Gd ) and Dy...
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Veröffentlicht in: | New journal of chemistry 2022-06, Vol.46 (24), p.11722-11733 |
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Zusammenfassung: | Three different sets of isomorphous dinuclear Gd/Dy complexes, [Ln
2
(L′)(acac)
4
]·2H
2
O·2CH
3
CN (Ln = Gd (
1
Gd
) and Dy (
2
Dy
); acac = acetylacetonate), [Ln
2
(L′)(tfac)
4
] (Ln = Gd (
3
Gd
) and Dy (
4
Dy
); tfac = trifluoroacetylacetonate), and [Ln
2
(L′)(hfac)
4
] (Ln = Gd (
5
Gd
) and Dy (
6
Dy
); hfac = hexafluoroacetylacetonate), where H
2
L′ is a new Ln-assisted
in situ
generated macrocyclic ligand from acyclic Schiff base HL, derived from a condensation reaction of 2,6-diformyl-4-methylphenol and
N
,
N
-dimethyldipropylenetriamine, have been synthesized by the reaction of lanthanide nitrates with ligand HL in the presence of different β-diketonate co-ligands. Structural analysis revealed that the lanthanide ions in these complexes are all eight-coordinated in a square antiprismatic geometry with
D
4d
symmetry. Magnetic measurements of these complexes revealed that the magnetic interaction between Gd
3+
ions is antiferromagnetic, while Dy
3+
ions are ferromagnetically coupled in dimetallic complexes, and the detailed analysis of Gd analogues discloses the significant influence of the different β-diketonate co-ligands on the magnitude of the magnetic interactions. All three Dy complexes exhibit zero field single-molecule magnet behaviour with energy barriers varying in the close range 60.1-62.8 K. The orientation of the magnetic axes and crystal structural parameters were critically analysed to establish magneto-structural correlations in three Dy-based SMMs to gain an in depth understanding of the magnetic dynamics in these systems.
Three different sets of isomorphous dinuclear Gd/Dy complexes with an uncommon macrocyclic ligand and β-diketonate co-ligands were reported in which Dy
2
analogues are zero field SMMs. |
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ISSN: | 1144-0546 1369-9261 |
DOI: | 10.1039/d2nj01017h |