Arsenic(III)-Capped 12-Tungsto-2-Arsenates(III) [M2(AsIIIW6O25)2(AsIIIOH)x]n- (M = CrIII, FeIII, ScIII, InIII, TiIV, MnII) and Their Magnetic Properties

Abstract

Six arsenic(III)-capped 12-tungsto-2-arsenates(III) of the type [M2(AsIIIW6O25)2(AsIIIOH)x]n- (M = CrIII, 1; FeIII, 2; ScIII, 3; InIII, 4; TiIV, 5; MnII, 6) have been synthesized in aqueous medium by direct reaction of the elements using a one-pot strategy and structurally characterized by FT-IR spectroscopy, single-crystal XRD, and elemental analysis. Polyanions 1-6 are comprised of two octahedrally coordinated guest metal ions M sandwiched between two {AsW6} units, resulting in a structure with C2h point-group symmetry. Polyanions 1-5 contain tri- and tetravalent metal ion guests M (M = CrIII, FeIII, ScIII, InIII, and TiIV, respectively), and they have one {AsIIIOH} group grafted on each {AsW6} unit, whereas the divalent MnII-containing derivative 6 has two such {AsIIIOH} groups grafted on each {AsW6} unit. Magnetic studies on polyanions 3-5 over the temperature range 1.8-295 K and magnetic fields of 0-7 T confirmed that they are diamagnetic. On the other hand, polyanions 1, 2, and 6 are strongly magnetic and follow the Curie-Weiss law above 30 K. The susceptibility plots of 1 and 6 exhibit broad peaks suggesting short-range antiferromagnetic ordering, while the very weak antiferromagnetic ordering of 2 is overshadowed by traces of a paramagnetic impurity. The magnetization data of 1, 2, and 6 at 1.8 K over 0-7 T were analyzed by using the Heisenberg exchange procedure. Small (negative) values of the obtained J values help in understanding the absence of long-range antiferromagnetic ordering.