Single-Crystal to Single-Crystal Reversible Transformations Induced by Thermal Dehydration in Keggin-Type Polyoxometalates Decorated with Copper(II)-Picolinate Complexes: The Structure Directing Role of Guanidinium

by / Thursday, 02 July 2015 / Published in

Single-Crystal to Single-Crystal Reversible Transformations Induced by Thermal Dehydration in Keggin-Type Polyoxometalates Decorated with Copper(II)-Picolinate Complexes: The Structure Directing Role of Guanidinium


Published in: Inorganics, 3(2), 194-218
2015/05/27
Publisher URL: http://www.mdpi.com/2304-6740/3/2/194
DOI: http://doi.org/10.3390/inorganics3020194 Authors:
Aroa Pache Santiago Reinoso Leire San Felices Amaia Iturrospe Luis Lezama Juan M. Gutiérrez-Zorrilla
Abstract:

Three new hybrid inorganic-metalorganic compounds containing Keggin-type polyoxometalates, neutral copper(II)-picolinate complexes and guanidinium cations have been synthesized in bench conditions and characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction: the isostructural [C(NH2)3]4[{XW12O40}{Cu2(pic)4}]·[Cu2(pic)4(H2O)]2·6H2O [X = Si (1), Ge (3)] and [C(NH2)3]8[{SiW12O40}2{Cu(pic)2}3{Cu2(pic)4(H2O)}2]·8H2O (2). The three compounds show a pronounced two-dimensional character owing to the structure-directing role of guanidinium. In 1 and 3, layers of [{XW12O40}{Cu2(pic)4}]n4n hybrid POM chains and layers of [Cu2(pic)4(H2O)] complexes and [C(NH2)3]+ cations pack alternately along the z axis. The hydrogen-bonding network established by guanidinium leads to a trihexagonal tiling arrangement of all copper(II)-picolinate species. In contrast, layers of [C(NH2)3]+-linked [{SiW12O40}2{Cu(pic)2}3]n8n double chains where each Keggin cluster displays a {Cu2(pic)4(H2O)} moiety pointing at the intralamellar space are observed in 2. The thermal stability of 13 has been studied by thermogravimetric analyses and variable temperature powder X-ray diffraction. Compounds 1 and 3 undergo single-crystal to single-crystal transformations promoted by reversible dehydration processes and the structures of the corresponding anhydrous phases 1a and 3a have been established. Despite the fact that the [Cu2(pic)4(H2O)] dimeric complexes split into [Cu(pic)2] monomers upon dehydration, the packing remains almost unaltered thanks to the preservation of the hydrogen-bonding network established by guanidinium and its associated Kagome-type lattice. Splitting of the dimeric complexes has been correlated with the electron paramagnetic resonance spectra.

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