Reversible and Topotactic Solvent Removal in a Magnetic
Ni(NCS)2 Coordination Polymer
Posted on 2017-06-28 - 11:35
Reaction
of Ni(NCS)2 with 4-(Boc-amino)pyridine in acetonitrile
leads to the formation of a new coordination polymer with the composition
Ni(NCS)2(4-(Boc-amino)pyridine)2·MeCN (1-MeCN). In the crystal structure the Ni(II) cations are linked
by the anionic ligands into chains that are further connected into
layers by intermolecular N–H···O hydrogen bonding.
These layers are stacked and channels are formed, in which acetonitrile
molecules are located. Solvent removal leads to the ansolvate 1, which shows microporosity as proven by sorption measurements.
Single crystal X-ray investigations reveal that the solvent removal
leads to a change in symmetry from primitive to C-centered, which is reversible and which proceeds via a topotactic
reaction leaving the network intact. The magnetic properties of 1-MeCN and 1 are governed by the ferromagnetic
exchange between spins of Ni(II) forming chains. The susceptibility
and specific heat for such a quantum Heisenberg chain of S = 1 spins with zero-field splitting are calculated using the DMRG
method and compared with the experimental results.
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Suckert, Stefan; Rams, Michał; Rams, Marek
M.; Näther, Christian (2017). Reversible and Topotactic Solvent Removal in a Magnetic
Ni(NCS)2 Coordination Polymer. ACS Publications. Collection. https://doi.org/10.1021/acs.inorgchem.7b00721
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AUTHORS (4)
SS
Stefan Suckert
MR
Michał Rams
MR
Marek
M. Rams
CN
Christian Näther