Three Banana-Shaped Arsenomolybdates Encapsulating a Hexanuclear Transition-Metal Central Magnetic Cluster: [AsIII2FeIII5MMo22O85(H2O)]n− (M = Fe3+, n = 14; M = Ni2+ and Mn2+, n = 15)

Abstract

Three polyoxometalates encapsulating high-nuclearity magnetic clusters MFe(5), [As(2)MFe(5)Mo(22)O(85)(H(2)O)](n-) (M = Fe(3+), n = 14; M = Ni(2+) and Mn(2+), n = 15), were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analysis, and magnetism measurements. The polyanion [As(2)MFe(5)Mo(22)O(85)(H(2)O)](n-) consists of a central MMo(7)O(28) (M = Fe(3+), Ni(2+), and Mn(2+)) fragment and two AsMo(7)O(27) fragments linked together by two trimeric clusters, Fe(2)MoO(μ(2)-O)(2) and Fe(3)(H(2)O), to form a banana-shaped structure with C(1) symmetry. The MMo(7)O(28) and AsMo(7)O(27) units have a similar structure and can be considered as a monocapped hexavacant α-B-Keggin subunit with a central MO(4) group or a central As(III)O(3) group. The polyoxometalates have a low absorption of υ(Mo-O(d)) (925-913 cm(-1)) because most of the Mo atoms in the polyanions have at least two longer Mo-O(d) bonds. The framework of the arsenomolybdates is stable before As(2)O(3) escaping (ca. 300 °C). The analysis of magnetostructural correlations and magnetism measurements indicate the coexistence of ferro- and antiferromagnetic interactions, which give an overall ferromagnetic spin ground state in the compounds.