title: New Perspectives for Old Clusters: Anderson-Evans Anions as Building Blocks of Large Polyoxometalate Frameworks in a Series of Heterometallic 3 d-4 f Species.
abstract: A series of nine [Sb7W36O133Ln3M2(OAc)(H2O)8](17-) heterometallic anions (Ln3M2; Ln=La-Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs-type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW9O33} capping unit formed by a planar {MW6O24} fragment to which three {WO2} groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the ɛ-Keggin cluster. It is shown, for the first time, that classical Anderson-Evans {MW6O24} anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk-shaped species is also revealed. The Ln3M2 anions possess chirality owing to a {Sb4O4} cluster being encapsulated in left- or right-handed orientations. Their ability to self-associate in blackberry-type vesicles in solution has been assessed for the Ce3Co2 derivative.
authors.affiliation: Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, P. O. Box 644, 48080, Bilbao, Spain.|BCMaterials, Parque Tecnológico de Bizkaia, Edificio 500, 48160, Derio, Spain.
authors.forename: Beñat
authors.initials: B
authors.lastname: Artetxe
authors.affiliation: Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, P. O. Box 644, 48080, Bilbao, Spain. santiago.reinoso@ehu.es.
authors.forename: Santiago
authors.initials: S
authors.lastname: Reinoso
authors.affiliation: Servicios Generales de Investigación SGIker, Universidad del País Vasco UPV/EHU, P. O. Box 644, 48080, Bilbao, Spain.
authors.forename: Leire
authors.initials: L
authors.lastname: San Felices
authors.affiliation: Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, P. O. Box 644, 48080, Bilbao, Spain.|BCMaterials, Parque Tecnológico de Bizkaia, Edificio 500, 48160, Derio, Spain.
authors.forename: Luis
authors.initials: L
authors.lastname: Lezama
authors.affiliation: Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, P. O. Box 644, 48080, Bilbao, Spain. juanma.zorrilla@ehu.es.|BCMaterials, Parque Tecnológico de Bizkaia, Edificio 500, 48160, Derio, Spain. juanma.zorrilla@ehu.es.
authors.forename: Juan M
authors.initials: JM
authors.lastname: Gutiérrez-Zorrilla
authors.affiliation: Serveis Centrals d'Instrumentació Científica, Universitat Jaume I, Avda. Sos Baynat s/n, 12071, Castellón de la Plana, Spain.
authors.forename: Cristian
authors.initials: C
authors.lastname: Vicent
authors.affiliation: Department of Polymer Science, The University of Akron, Akron, OH, 44325-3909, USA.
authors.forename: Fadi
authors.initials: F
authors.lastname: Haso
authors.affiliation: Department of Polymer Science, The University of Akron, Akron, OH, 44325-3909, USA.
authors.forename: Tianbo
authors.initials: T
authors.lastname: Liu
mesh_terms: D000838:Anions / Q000737:chemistry*; D002563:Cerium / Q000737:chemistry*; D018360:Crystallography, X-Ray; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D017973:Tungsten Compounds / Q000737:chemistry*; D000099294:Polyoxometalates
chemical_list: D000838:Anions; D002563:Cerium; D028581:Lanthanoid Series Elements; D009942:Organometallic Compounds; D017973:Tungsten Compounds; C102296:polyoxometalate I; D000099294:Polyoxometalates
keywords: X-ray diffraction; cluster compounds; polyoxometalates; self-assembly; supramolecular chemistry