title: Nanoporosity, Inclusion Chemistry, and Spin Crossover in Orthogonally Interlocked Two-Dimensional Metal-Organic Frameworks.
abstract: [Fe(tvp)2 (NCS)2 ] (1) (tvp=trans-(4,4'-vinylenedipyridine)) consists of two independent perpendicular stacks of mutually interpenetrated two-dimensional grids. This uncommon supramolecular conformation defines square-sectional nanochannels (diagonal≈2.2 nm) in which inclusion molecules are located. The guest-loaded framework 1@guest displays complete thermal spin-crossover (SCO) behavior with the characteristic temperature T1/2 dependent on the guest molecule, whereas the guest-free species 1 is paramagnetic whatever the temperature. For the benzene-guest derivatives, the characteristic SCO temperature T1/2 decreases as the Hammet σp parameter increases. In general, the 1@guest series shows large entropy variations associated with the SCO and conformational changes of the interpenetrated grids that leads to a crystallographic-phase transition when the guest is benzonitrile or acetonitrile/H2 O.
authors.affiliation: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, 46980 Paterna, Valencia (Spain).
authors.forename: Tania
authors.initials: T
authors.lastname: Romero-Morcillo
authors.affiliation: Departamento de Física de la Materia Condensada, Universidad del Pais Vasco UPV/EHU, 48080 Bilbao (Spain).
authors.forename: Noelia
authors.initials: N
authors.lastname: De la Pinta
authors.affiliation: Unidad de Siderurgia, Fundación Tecnalia R&I, 48160 Derio (Spain).
authors.forename: Lorena M
authors.initials: LM
authors.lastname: Callejo
authors.affiliation: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, 46980 Paterna, Valencia (Spain).
authors.forename: Lucía
authors.initials: L
authors.lastname: Piñeiro-López
authors.affiliation: Departamento de Física Aplicada, Universitat Politècnica de València, 46022 Valencia (Spain).
authors.forename: M Carmen
authors.initials: MC
authors.lastname: Muñoz
authors.affiliation: Departamento de Física de la Materia Condensada, Universidad del Pais Vasco UPV/EHU, 48080 Bilbao (Spain).
authors.forename: Gotzon
authors.initials: G
authors.lastname: Madariaga
authors.affiliation: Departamento de Química Inorgánica, Universidad de Valencia, 46100 Burjassot, Valencia (Spain).
authors.forename: Sacramento
authors.initials: S
authors.lastname: Ferrer
authors.affiliation: Departamento de Física Aplicada II, Universidad del Pais Vasco UPV/EHU, 48080 Bilbao (Spain).
authors.forename: Tomasz
authors.initials: T
authors.lastname: Breczewski
authors.affiliation: Departamento de Química Inorgánica, Universidad del Pais Vasco UPV/EHU, 48080 Bilbao (Spain). roberto.cortes@ehu.es.
authors.forename: Roberto
authors.initials: R
authors.lastname: Cortés
authors.affiliation: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, 46980 Paterna, Valencia (Spain). jose.a.real@uv.es.
authors.forename: José A
authors.initials: JA
authors.lastname: Real
keywords: inclusion compounds; interpenetration; iron; metal-organic frameworks; spin crossover