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RESEARCH PRODUCT

Nanoporosity, Inclusion Chemistry, and Spin Crossover in Orthogonally Interlocked Two-Dimensional Metal-Organic Frameworks

Lorena M. CallejoGotzon MadariagaTomasz BreczewskiNoelia De La PintaTania Romero-morcilloSacramento FerrerM. Carmen MuñozLucía Piñeiro-lópezJosé Antonio RealRoberto Cortés

subject

StereochemistryIronOrganic ChemistrySupramolecular chemistryInclusion compoundsInterpenetrationGeneral ChemistryMetal-organic frameworksSpin crossoverCatalysischemistry.chemical_compoundParamagnetismCrystallographyBenzonitrilechemistrySpin crossoverFISICA APLICADAPerpendicularMoleculeMetal-organic frameworkAcetonitrile

description

[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 approximate to 2.2nm) in which inclusion molecules are located. The guest-loaded framework 1@guest displays complete thermal spin-crossover (SCO) behavior with the characteristic temperature T-1/2 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 T-1/2 decreases as the Hammet sigma(p) 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/H2O.

yearjournalcountryeditionlanguage
2015-01-23Chemistry - A European Journal
https://doi.org/10.1002/chem.201500310