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Open AccessArticle

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

1
Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, P. O. Box 644, Bilbao 48080, Spain
2
Servicios Generales de Investigación SGIker, Universidad del País Vasco UPV/EHU, P. O. Box 644, Bilbao 48080, Spain
3
BCMaterials, Parque Científico y Tecnológico de Bizkaia, Edificio 500, Derio 48160, Spain
*
Authors to whom correspondence should be addressed.
Academic Editors: Greta Ricarda Patzke and Pierre-Emmanuel Car
Inorganics 2015, 3(2), 194-218; https://doi.org/10.3390/inorganics3020194
Received: 13 April 2015 / Accepted: 19 May 2015 / Published: 27 May 2015
(This article belongs to the Special Issue Polyoxometalates)
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. View Full-Text
Keywords: polyoxometalates; crystal-to-crystal transformations; guanidinium polyoxometalates; crystal-to-crystal transformations; guanidinium
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MDPI and ACS Style

Pache, A.; Reinoso, S.; Felices, L.S.; Iturrospe, A.; Lezama, L.; Gutiérrez-Zorrilla, J.M. 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. Inorganics 2015, 3, 194-218. https://doi.org/10.3390/inorganics3020194

AMA Style

Pache A, Reinoso S, Felices LS, Iturrospe A, Lezama L, Gutiérrez-Zorrilla JM. 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. Inorganics. 2015; 3(2):194-218. https://doi.org/10.3390/inorganics3020194

Chicago/Turabian Style

Pache, Aroa; Reinoso, Santiago; Felices, Leire S.; Iturrospe, Amaia; Lezama, Luis; Gutiérrez-Zorrilla, Juan M. 2015. "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" Inorganics 3, no. 2: 194-218. https://doi.org/10.3390/inorganics3020194

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