In search of 3d/4f-metal single-molecule magnets: Nickel(II)/lanthanide(III) coordination clusters

Polyzou, Christina D.; Efthymiou, Constantinos G.; Escuer, Albert; Cunha-Silva, Luı́s; Papatriantafyllopoulou, Constantina; Perlepes, Spyros P.

doi:10.1351/pac-con-12-09-08

Cited by 37 publications

(28 citation statements)

References 69 publications

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“…We have developed an intense interest in the synthesis of 3d/4f metal clusters by the employment of various pyridyl oximate-and alkoxide-containing ligands; these research efforts have yielded a variety of new mixed-metal species with interesting structural features and magnetic properties, including Ni 8 Dy 8 [38,39], Ni 2 Ln 2 [40], Ni 3 Ln [26], Ni 2 Ln [36,37,40], Mn 4 Ln 2 [41], etc. Restricting further discussion to the use of (py) 2 CO in this field, we recently reported the first Mn/4f compounds, which belong to a family of cross-shaped Mn 4 Ln 2 clusters, where some of them exhibit slow relaxation of magnetization; whereas, in the past, we reported the first Ni/4f compounds with the monoanionic form of (py) 2 CO. Wishing to expand this work, we recently decided to investigate the previously unexplored reaction system of Co 2+ /Ln 3+ /(py) 2 CO.…”

Section: Synthetic Commentsmentioning

confidence: 99%

A Novel Family of Triangular CoII2LnIII and CoII2YIII Clusters by the Employment of Di-2-Pyridyl Ketone

et al. 2019

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The synthesis, structural characterization and magnetic study of novel Co II /4f and Co II /Y III clusters are described. In particular, the initial employment of di-2-pyridyl ketone, (py) 2 CO, in mixed metal Co/4f chemistry, provided access to four triangular clusters,is the monoanion of the hemiketal form of (py) 2 CO. Clusters 1-4 are the first reported Co/4f (1-3) and Co/Y (4) species bearing (py) 2 CO or its derivatives, despite the fact that over 200 metal clusters bearing this ligand have been reported so far. Variable-temperature, solid-state dc and ac magnetic susceptibility studies were carried out on 1-4 and revealed the presence of weak ferromagnetic exchange interactions between the metal ions (J Co-Co = +1.3 and +0.40 cm −1 in 1 and 4, respectively; J Co-Gd = +0.09 cm −1 in 1). The ac susceptibility studies on 2 revealed nonzero, weak out-of-phase (χ" M ) signals below~5 K.

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Section: Synthetic Commentsmentioning

confidence: 99%

A Novel Family of Triangular CoII2LnIII and CoII2YIII Clusters by the Employment of Di-2-Pyridyl Ketone

et al. 2019

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“…Thus, it is essential that ligands with high bridging capability that have the potential to lead to species with unprecedented metal topologies and/or high nuclearity SBUs be introduced into this field; to this purpose, we decided to use 2-pyridyl oximes for the isolation and characterization of new MOFs and coordination polymers. 2-pyridyl oximes is a family of ligands that have been extensively used in metal cluster chemistry due to their ability to bridge a large number of metal ions and, often, promote ferromagnetic interactions between the metal centers [ 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 ]. Although the use of such ligands has led to significant breakthroughs in the areas of single-molecule and single-chain magnetism, they have never been employed for MOF synthesis [ 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 ].…”

Section: Introductionmentioning

confidence: 99%

From 1D Coordination Polymers to Metal Organic Frameworks by the Use of 2-Pyridyl Oximes

et al. 2020

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The synthesis and characterization of coordination polymers and metal–organic frameworks (MOFs) has attracted a significant interest over the last decades due to their fascinating physical properties, as well as their use in a wide range of technological, environmental, and biomedical applications. The initial use of 2-pyridyl oximic ligands such as pyridine-2 amidoxime (H2pyaox) and 2-methyl pyridyl ketoxime (Hmpko) in combination with 1,2,4,5-benzene tetracarboxylic acid (pyromellitic acid), H4pma, provided access to nine new compounds whose structures and properties are discussed in detail. Among them, [Zn2(pma)(H2pyaox)2(H2O)2]n (3) and [Cu4(OH)2(pma)(mpko)2]n (9) are the first MOFs based on a 2-pyridyl oxime with 9 possessing a novel 3,4,5,8-c net topology. [Zn2(pma)(H2pyaox)2]n (2), [Cu2(pma)(H2pyaox)2(DMF)2]n (6), and [Cu2(pma)(Hmpko)2(DMF)2]n (8) join a small family of coordination polymers containing an oximic ligand. 9 exhibits selectivity for FeIII ions adsorption, as was demonstrated by a variety of techniques including UV-vis, EDX, and magnetism. DC magnetic susceptibility studies in 9 revealed the presence of strong antiferromagnetic interactions between the metal centers, which lead to a diamagnetic ground state; it was also found that the magnetic properties of 9 are affected by the amount of the encapsulated Fe3+ ions, which is a very desirable property for the development of magnetism-based sensors.

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“…Transition metal – lanthanides(3d–4f) mixed metal complexes have gained increased attention in the recent past due to their exotic applications in the magnetism, fluorescent sensors and catalysis . The most important reason to chemists for continuous synthesis of mixed metal complexes is due to the urge to explore highly interesting magneto‐chemistry such as construction of Single‐molecule magnets (SMMs), magnetic refrigerants, 3D molecule based magnets and single chain magnets . The SMMs have been in the forefront of magneto‐chemistry due to their potential applications in the data processing and storage on nano‐size magnetic devices.…”

Section: Introductionmentioning

confidence: 99%

A Series of Umbrella‐Shape Copper‐Lanthanides Based Mixed Metallic Coordination Complexes

et al. 2019

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A series of six hetero‐bimetallic complexes having umbrella shape topology and general formula (L)2CuLn(NO3)(Ph3PO) have been synthesized by reacting a methanolic solution of diprotic ligand (H2L) [(E)‐2‐(((2‐hydroxyphenyl)imino)methyl)‐6‐methoxyphenol] and co‐ligand Ph3P=O with CuCl2.2H2O and Ln(NO3)3⋅6H2O (Ln= Gd(1), Tb(2),Dy(3), Ho(4), Er(5) and Y(6)) in the presence of triethylamine base. The iso‐structural complexes (1‐6) have been characterized by Single crystal XRD measurement. Elemental analysis, EPR, IR and UV/Vis spectra have been recorded to further characterise these complexes. The direct current (dc) and alternating current (ac) magnetic susceptibility measurements has been carried out to study magnetic properties of the complexes. Thermogravimetric analysis (TGA) has also been done to assess thermal stability of the complexes.

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In search of 3d/4f-metal single-molecule magnets: Nickel(II)/lanthanide(III) coordination clusters

Cited by 37 publications

References 69 publications

A Novel Family of Triangular CoII2LnIII and CoII2YIII Clusters by the Employment of Di-2-Pyridyl Ketone

A Novel Family of Triangular CoII2LnIII and CoII2YIII Clusters by the Employment of Di-2-Pyridyl Ketone

From 1D Coordination Polymers to Metal Organic Frameworks by the Use of 2-Pyridyl Oximes

A Series of Umbrella‐Shape Copper‐Lanthanides Based Mixed Metallic Coordination Complexes

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