title: Electronic Structure Studies on the Whole Keplerate Family: Predicting New Members.
abstract: A comprehensive study of the electronic structure of nanoscale molecular oxide capsules of the type [{MVI(MVI)5O21}12{M'V2O2(μ-X)(μ-Y)(Ln-)}30](12+n)-is presented, where M,M'=Mo,W, and the bridging ligands X,Y=O,S, carried out by means of density functional theory. Discussion of the electronic structure of these derivatives is focused on the thermodynamic stability of each of the structures, the one having the highest HOMO-LUMO gap being M=W, M'=Mo, X=Y=S. For the most well-known structure M=M'=Mo, X=Y=O, [Mo132O372]12-, the chemical bonding of several ligands to the {MoV2O2(μ-O)2} linker moiety produces negligible effects on its stability, which is evidence of a strong ionic component in these bonds. The existence of a hitherto unknown species, namely W132with both bridging alternatives, is discussed and put into context.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. dels Països Catalans, 16, 43007, Tarragona, Spain.
authors.forename: Dolores
authors.identifier: http://orcid.org/0000-0002-2936-6749
authors.initials: D
authors.lastname: Melgar
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. dels Països Catalans, 16, 43007, Tarragona, Spain.
authors.forename: Nuno A G
authors.identifier: http://orcid.org/0000-0002-5754-7328
authors.initials: NAG
authors.lastname: Bandeira
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. dels Països Catalans, 16, 43007, Tarragona, Spain.|Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Av. dels Països Catalans, 26, 43007, Tarragona, Spain.
authors.forename: Carles
authors.identifier: http://orcid.org/0000-0001-9581-2922
authors.initials: C
authors.lastname: Bo
keywords: cage compounds; computational chemistry; density functional calculations; electronic structure; nanocapsules; polyoxometalates