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Nanoporosity, Inclusion Chemistry, and Spin Crossover in Orthogonally Interlocked Two‐Dimensional Metal–Organic Frameworks
Author(s) -
RomeroMorcillo Tania,
De la Pinta Noelia,
Callejo Lorena M.,
PiñeiroLópez Lucía,
Muñoz M. Carmen,
Madariaga Gotzon,
Ferrer Sacramento,
Breczewski Tomasz,
Cortés Roberto,
Real José A.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500310
Subject(s) - spin crossover , supramolecular chemistry , chemistry , molecule , benzonitrile , crystallography , acetonitrile , paramagnetism , nitrile , crystal structure , condensed matter physics , physics , organic chemistry
[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 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 σ 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/H 2 O.