dc.contributor.author | Pache Legarreta, Aroa | |
dc.contributor.author | Reinoso Crespo, Santiago | |
dc.contributor.author | San Felices Mateos, Leire | |
dc.contributor.author | Iturrospe Ibarra, Amaia | |
dc.contributor.author | Lezama Diago, Luis María | |
dc.contributor.author | Gutiérrez Zorrilla López, Juan Manuel | |
dc.date.accessioned | 2019-02-22T19:37:13Z | |
dc.date.available | 2019-02-22T19:37:13Z | |
dc.date.issued | 2015-05-27 | |
dc.identifier.citation | Inorganics 3 : 194-218 (2015) | es_ES |
dc.identifier.issn | 2304-6740 | |
dc.identifier.uri | http://hdl.handle.net/10810/31668 | |
dc.description.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}{Cu-2(pic)(4)}] . [Cu-2(pic)(4)(H2O)](2) .6H(2)O [X = Si (1), Ge (3)] and [C(NH2)(3)]8[{SiW12O40}(2){Cu(pic)(2)}3{Cu-2(pic)4(H2O)}(2)] .8H(2)O (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}{Cu-2(pic)(4)}] n(4n-) hybrid POM chains and layers of [Cu-2(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)] n(8n-) double chains where each Keggin cluster displays a {Cu-2(pic)(4)(H2O)} moiety pointing at the intralamellar space are observed in 2. The thermal stability of 1-3 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 [Cu-2(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. | es_ES |
dc.description.sponsorship | This work was funded by Eusko Jaurlaritza/Gobierno Vasco (grant IT477- 10 and predoctoral fellowship to A. P.), Ministerio de Economia y Competitividad (grant MAT2013-48366-C2-2P) and Universidad del Pais Vasco UPV/EHU (grant UFI11/53). Technical and human support provided by SGIker (UPV/EHU) is gratefully acknowledged. | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | MDPI | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/MAT2013-48366-C2-2P | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by/3.0/es/ | * |
dc.subject | polyoxometalates | es_ES |
dc.subject | crystal-to-crystal transformations | es_ES |
dc.subject | guanidinium | es_ES |
dc.title | 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 | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.relation.publisherversion | https://www.mdpi.com/2304-6740/3/2/194 | es_ES |
dc.identifier.doi | 10.3390/inorganics3020194 | |
dc.departamentoes | Química inorgánica | es_ES |
dc.departamentoeu | Kimika ez-organikoa | es_ES |