Thermostructural behavior in a series of lanthanide-containing polyoxotungstate hybrids with copper(II) complexes of the tetraazamacrocycle cyclam: a single-crystal-to-single-crystal transformation study
| dc.contributor.author | Martín Caballero, Jagoba | |
| dc.contributor.author | Artetxe, Beñat | |
| dc.contributor.author | Reinoso, Santiago | |
| dc.contributor.author | San Felices, Leire | |
| dc.contributor.author | Vitoria, Pablo | |
| dc.contributor.author | Larrañaga, Aitor | |
| dc.contributor.author | Vilas, José Luis | |
| dc.contributor.author | Gutiérrez Zorrilla, Juan M. | |
| dc.contributor.department | Institute for Advanced Materials and Mathematics - INAMAT2 | en |
| dc.contributor.funder | Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa | es |
| dc.date.accessioned | 2020-01-15T11:54:53Z | |
| dc.date.available | 2020-03-14T00:00:13Z | |
| dc.date.issued | 2019 | |
| dc.description.abstract | A series of 14 isostructural [Cu(cyclam)](2)[{Cu(cyclam)}4{(a-GeW11O39)Ln(H2O)-(OAc)(12)].18H(2)O (1-Ln, where Ln = La Lu; cyclam = 1,4,8,11-tetraazacyclotetradecane) polyoxometalate-based hybrids reported herein represent (i) the first example of a twodimensional covalent hybrid lattice involving the [{(aXWI 1039)Ln(H2O)(OAc)}2in- archetype and (ii) the first structural characterization of such a dimeric polyoxotungste for Ln = La and Pr as well as for the combination of X = Ge and Ln = Ce, Nd, Sm, or Lu. Compounds 1-Ln have been characterized by elemental analyses, infrared spectroscopy, and thermogravimetric analysis, and their thermostructural behavior has been monitored by powder and single-crystal Xray diffraction. The title compounds undergo two single-crystal-to-single-crystal transformations triggered dehydration leading to the [{Cu(cydam)}6{(alpha-GeW11O39)Ln(H2O)(OAc)}2]-4H(2)O intermediate (2-Ln, where Ln = Eu or Er) and [Cu(cyclam)]0.5[{Cu(cyclam)}55{(alpha-GeW11O39)Ln(0Ac)}2] (3-Ln, where Ln = Ce or Eu) final anhydrous phases, the latter evidencing a coordinatively unsaturated derivative of the dimeric archetype for the first time. These transitions involve formation and disruption of Cu Opom bonds that result in different {Cu(cydam)}(2+) moieties grafting onto and being released from Keggin surfaces, which reduces the dimensionality of 1-Ln to one-dimensional covalent assemblies for 2-Ln and 3-Ln. While all 3-Ln phases rehydrate fully upon exposure to air for 24 h, the kinetics governing the crystal transitions back toward 1Ln through 2-Ln depend on the nature of Ln. Under ambient moisture, the anhydrous structures fully revert back to the parent framework for Ln = La Sm, while the samples containing Eu to Lu afford mixtures of 1-Ln and 2-Ln and require immersion in water for the structural reversion to reach completion. Single-crystal X-ray diffraction analyses of the rehydrated 1R-Ln samples (Ln = Ce, Eu, and Er) support these observations. | en |
| dc.description.sponsorship | This work was funded by Eusko Jaurlaritza/Gobierno Vasco (Grant PIBA2018-59 and ELKARTEK bG18 10(2018/00054), MINECO (Grant MAT2017-89553-P), and UPV/EHU (Grants PPG17/37 and GIU17/050). S.R. thanks Obra Social la Caixa, Fundacion Caja Navarra, and UPNA for a research contract in the framework of the program "Captación del Talento". Technical and human support provided by SGIker (UPV/EHU) is gratefully acknowledged. | en |
| dc.embargo.lift | 2020-03-14 | |
| dc.embargo.terms | 2020-03-14 | |
| dc.format.extent | 13 p. | |
| dc.format.mimetype | application/pdf | en |
| dc.identifier.doi | 10.1021/acs.inorgchem.8b03471 | |
| dc.identifier.issn | 0020-1669 | |
| dc.identifier.uri | https://academica-e.unavarra.es/handle/2454/36076 | |
| dc.language.iso | eng | en |
| dc.publisher | American Chemical Society | en |
| dc.relation.ispartof | Inorganic Chemistry, 58 (7), 4365-4375 | en |
| dc.relation.projectID | info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2017-89553-P/ES/ | |
| dc.relation.publisherversion | https://doi.org/10.1021/acs.inorgchem.8b03471 | |
| dc.rights | © 2019 American Chemical Society | en |
| dc.rights.accessRights | info:eu-repo/semantics/openAccess | |
| dc.subject | Crystals | en |
| dc.subject | Ligands | en |
| dc.subject | Ions | en |
| dc.subject | Physical and chemical processes | en |
| dc.subject | Phase transitions | en |
| dc.title | Thermostructural behavior in a series of lanthanide-containing polyoxotungstate hybrids with copper(II) complexes of the tetraazamacrocycle cyclam: a single-crystal-to-single-crystal transformation study | en |
| dc.type | info:eu-repo/semantics/article | |
| dc.type.version | info:eu-repo/semantics/acceptedVersion | |
| dspace.entity.type | Publication | |
| relation.isAuthorOfPublication | 46bbf241-764d-4c78-9667-4c307cf84092 | |
| relation.isAuthorOfPublication.latestForDiscovery | 46bbf241-764d-4c78-9667-4c307cf84092 |