Nanoporosity, Inclusion Chemistry, and Spin Crossover in Orthogonally Interlocked Two‐Dimensional Metal–Organic Frameworks. Issue 34 (15th July 2015)

• Record Type: Journal Article
• Authors: Romero‐Morcillo, Tania; De la Pinta, Noelia; Callejo, Lorena M.; Piñeiro‐López, Lucía; Muñoz, M. Carmen; Madariaga, Gotzon; Ferrer, Sacramento; Breczewski, Tomasz; Cortés, Roberto; Real, José A.
• Is Part Of: Chemistry. Volume 21:Issue 34(2015)
• Page Start: 12112
• Page End: 12120
• Publication Date: 2015-07-15
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201500310
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>[Fe(tvp)₂(NCS)₂] (<bold>1</bold>) (tvp=<italic>trans</italic>‐(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 <bold>1@guest</bold> displays complete thermal spin‐crossover (SCO) behavior with the characteristic temperature <italic>T</italic>_1/2 dependent on the guest molecule, whereas the guest‐free species <bold>1</bold> is paramagnetic whatever the temperature. For the benzene–guest derivatives, the characteristic SCO temperature <italic>T</italic>_1/2 decreases as the Hammet <italic>σ</italic>_p parameter increases. In general, the <bold>1@guest</bold> 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/H₂O.</p> </abstract>