A Series of Banana-Shaped 3d-4f Heterometallic Cluster Substituted Polyoxometalates: Syntheses, Crystal Structures, and Magnetic Properties

Abstract

Four seven-nuclearity 3d-4f heterometallic cluster {FeLnO} substituted polyoxometalates (HPz)KFeLn(μ-O)(B-α-GeWO)(GeWO)· xHO (1-Ln, Pz = piperazine, Ln = Tb, Dy, Ho, Er for x = 27, 25, 25, 24, respectively) have been hydrothermally prepared and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectrometry, thermogravimetric analyses, elemental analyses, and electrospray ionization mass spectrometry. Single-crystal X-ray diffraction analyses revealed that 1-Ln contain an unprecedented banana-shaped polyanion constructed from an iron-lanthanide heterometallic {FeLnO} cluster, two trilacunary {B-α-GeWO} units, and one hexalacunary {GeWO} fragment. The magnetic susceptibility surveying proved the presence of antiferromagnetic coupling in 1-Ln.

A Series of High‐nuclear 3d‐4f (FeIII8LnIII2) Complexes: Syntheses, Structures, and Magnetic Properties

“…In this case, the combination of 3 d and 4 f ions may be an effective strategy, because the intermediate magnetic exchange between 3 d ‐4 f ions may generate both a high‐spin state and magnetic anisotropy and improve the energy barrier U eff for spin reversal. Consequently, a lot of 3 d ‐4 f complexes showing SMM behaviors have been reported . The most attentions are focused on [Cu‐Ln], [Mn‐Ln] systems, and [Fe‐Ln] SMMs are less developed.…”

Single‐Molecule Magnetic, Catalytic and Photoluminescence Properties of Heterometallic 3d–4f [Ln{PZn2W10O38(H2O)2}2]11− Tungstophosphate Nanoclusters

“…However, several compounds of such heterometallic class were isolated, in which most of the reported compounds are organic‐inorganic hybrids which were synthesized by using organic ligands mostly under hydrothermal conditions with a few examples reported under mild conditions [8] . There are also some examples in which both 3 d and 4 f metals are present within the POM skeleton [9–17] . The heterometallic POM based on lone‐pair containing tungstoantimonates (III) were also reported by Artetxe et al .…”

Giant Ln 30 -Cluster-Embedded Polyoxotungstate Nanoclusters with Exceptional Proton-Conducting and Luminescent Properties

“…To balance charges, thirty-eight protons should be added to 1Ln, which can not be located and are assumed to be delocalized on the overall cluster structures, which are common in POMs. [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] Given Ln 30 W 107 are isomers, the detailed structural description will be provided only for Eu 30 W 107 . One uncommon feature of Eu 30 W 107 is that its outmost shell consists of as many as ten dilacunary POTs.…”