Exploiting the linking propensity of a water encapsulated POV cluster anion [As6V15O42(H2O)]6− towards lanthanide cations: Syntheses, crystal structures and thermal properties of [{M(H2O)7}2(As6V15O42(H2O)]·xH2O (M = La3+, Sm3+ and Ce3+; x = 12, 13 and 11

The polyoxovanadate cluster anion [As6V15O42(H2O)]6−, an well known magnetic object, has been reacted with lanthanide ions (namely La3+, Sm3+ and Ce3+ ions) in a controlled synthesis resulting in the formation of a new series of coordination polymers [{La(H2O)7}2As6V15O42(H2O)]·12H2O (2), [{Sm(H2O)7}2As6V15O42(H2O)]·13H2O (3) and [{Ce(H2O)7}2 As6V15O42(H2O)]·11H2O (4). In compounds 2, 3 and 4, the high nuclearity spin cluster [As6V15O42(H2O)]6− acts as a tetradentate ligand with terminal oxo groups (VO) as donor centers. Compounds 2–4 are characterized by elemental and routine spectroscopic analyses and finally by single crystal X-ray structure determination. Compounds 2–4 are isomorphous in which each {V15} cluster anion is coordinated to four Ln3+ ion through its terminal oxygen atoms and each Ln3+ ion is coordinated to two cluster anions and seven water molecules satisfying the coordination number of nine around a lanthanide cation. In the crystal structure, the non-coordinated (lattice) water molecules, lanthanum-coordinated water molecules and VOt oxygen atoms (Ot = terminal oxygen) are involved in O–H···O hydrogen bonding interactions. The hydrogen bonding distances are measured as O···O separations, since hydrogen atoms could not be located in the crystal structures. The hydrogen bonding distances are varied in the range of 2.640–3.000 Å. The title compounds are additionally characterized by thermogravimetric analysis.

Graphical abstractCompound [H6As6V15O42(H2O)]·9H2O (1) has been reacted with lanthanide ions (namely La3+, Sm3+ and Ce3+ ions) in a controlled synthesis resulting in the formation of a new series of coordination polymers [{La(H2O)7}2V15As6O42(H2O)]·12H2O (2), [{Sm(H2O)7}2V15As6O42(H2O)]·13H2O (3) and [{Ce(H2O)7}2V15As6O42(H2O)]·11H2O (4), respectively. Compounds 2–4 are isostructural in which each {V15} cluster anion is coordinated to four Ln3+ ion through its terminal oxygen atoms and each Ln3+ ion is coordinated to two cluster anions and seven water molecules satisfying the coordination number of nine around a lanthanide cation.Figure optionsDownload full-size imageDownload as PowerPoint slide