A novel two-dimensional (2D) coordination polymer, [Co(ppad)2]n (1), resulted from the assembly of Co(II) ions based on a versatile ligand termed N(3)-(3-pyridoyl)-3-pyridinecarboxamidrazone. Alternating/direct-current magnetic studies of compound 1 indicate that the spatially separated high-spin Co(II) ions act as single-ion magnets (SIMs). The present work represents the first case of a 2D Co(II)-based SIM composed of a monocomponent organic spacer.
Stable Ln(iii)-MOFs with a versatile 2-(4-pyridyl)-terephthalic acid ligand can be used as a multifunctional sensing platform for Fe3+, Cr2O72−, and nitrofuran detection.
Two β-diketone mononuclear Dy(III) compounds, formulated as Dy(BTFA)(HO) (1) and Dy(BTFA)(bpy) (2) (BTFA = 3-benzoyl-1,1,1-trifluoroacetone, bpy = 2,2'-bipyridine), were prepared. Compound 1 can be identified to transform to 2 in the attendance of bpy coligand, when the local geometry symmetry of eight-coordinated Dy(III) ion changes from a dodecahedron (D) in 1 to a square antiprism (D) in 2. Fine-tuning structure aroused by auxiliary ligand has dramatical impact on magnetic properties of compounds 1 and 2. Magnetic investigations demonstrate that both 1 and 2 display dynamic magnetic relaxation of single-molecule magnets (SMMs) behavior with different effective barriers (ΔE/k) of 93.09 K for 1 under zero direct-current (DC) field as well as 296.50 K for 1 and 151.01 K for 2 under 1200 Oe DC field, respectively. As noticed, compound 1 possesses higher effective barrier than 2, despite 1 exhibiting a lower geometrical symmetry of the Dy(III) ion. Ab initio studies reveal that the Kramers doublet ground state is predominantly axial with the g tensors of two compounds matching the Ising-limit factor of 20 anticipated for the pure M = ±15/2 state. Electrostatic analysis confirms the uniaxial anisotropy directions, highlighting that the proper electrostatic distribution of the coordination sphere around Ln(III) center is the critical factor to improve the magnetic anisotropy and determine the dynamic behaviors of SMMs.
By means of the facile
chemistry, structural assembly, and transformation of four mononuclear
Dy(III) complexes, Dy(bpad)3·CH3OH·H2O (1), Dy(bpad)2(H2O)2·NO3 (2), [Dy(bpad)2(tmhd)] (3), and [Dy(bpad)2(btfa)] (4) (Hbpad = N3-benzoylpyridine-2-carboxamidrazone,
tmhd = 2,2,6,6-tetramethylheptane-3,5-dione, btfa = 3-benzoyl-1,1,1-trifluoroacetone),
with distinct architectures and local symmetries were established.
The disparity of the coordination geometries around the Dy(III) ion
among these complexes impacts the strength of the crystal field and
the local tensor of anisotropy (D) of each Dy site
and their relative orientations, therefore giving rise to diverse
SIM behaviors with distinguishing relaxation energy barriers of 106.93
K for 1, 52.55 K for 2, 48.16 K for 3, and 51.41 K for 4. The differences of the
magnetic property and the magnetic anisotropy for four complexes have
been explained by ab initio calculations, which are
corresponding to the experimental results.
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