American Chemical Society
ic5b02772_si_003.cif (2.52 MB)

Lanthanoid Template Isolation of the α‑1,5 Isomer of Dicobalt(II)-Substituted Keggin Type Phosphotungstates: Syntheses, Characterization, and Magnetic Properties

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posted on 2016-08-10, 11:38 authored by Rakesh Gupta, Firasat Hussain, Masahiro Sadakane, Chisato Kato, Katsuya Inoue, Sadafumi Nishihara
A new series of heterometallic 3d–4f sandwich type phosphotungstates, [Ln­{PCo2W10O38(H2O)2}2]11– (Ln = SmIII, EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII, YbIII, and LuIII, denoted 1a–10a, respectively), have been synthesized by a one-pot reaction procedure on reacting the dilacunary K14[P2W19O69(H2O)]·24H2O precursor with Ln­(NO3)3·nH2O and Co­(NO3)2·6H2O in an aqueous potassium chloride solution. All the compounds were isolated as potassium salts and further characterized with different analytical techniques such as single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, high-resolution electrospray ionization mass spectrometry, elemental analysis by inductively coupled plasma atomic emission spectroscopy, magnetic measurement, and thermogravimetric analysis. Single-crystal X-ray diffraction analysis of the compounds reveals that all these compounds are isostructural and crystallized in the orthorhombic crystal system in space group Iba2. The polyanions contain the α-1,5 isomer of dicobalt-substituted α-Keggin phosphotungstate, which sandwiched lanthanoid cation and formed novel heterometallic dimer species. The temperature-dependent magnetic susceptibilities of 1a, 2a, 4a, and 7a–10a indicate the dominant contribution of the ferromagnetic interaction between CoII and CoII within the cluster, while the antiferromagnetic interaction between CoII and LnIII dominates for 3a, 5a, and 6a. The isothermal magnetizations of 1a–10a show a gradual increase in magnetization at low fields and do not reach saturation even at 50 kOe.