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@ARTICLE{Ghisolfi:201881,
author = {Ghisolfi, Alessio and Monakhov, Kirill Yu. and Pattacini,
Roberto and Braunstein, Pierre and López, Xavier and de
Graaf, Coen and Speldrich, Manfred and van Leusen, Jan and
Schilder, Helmut and Kögerler, Paul},
title = {{A} comparative synthetic, magnetic and theoretical study
of functional {M}$_{4}${C}l $_{4}$ cubane-type {C}o(ii) and
{N}i(ii) complexes},
journal = {Dalton transactions},
volume = {43},
number = {21},
issn = {1477-9234},
address = {London},
publisher = {Soc.},
reportid = {FZJ-2015-04175},
pages = {7847 -},
year = {2014},
abstract = {We describe the synthesis, structures, and magnetochemistry
of new M4Cl4 cubane-type cobalt(II) and nickel(II) complexes
with the formula [M(μ3-Cl)Cl(HL·S)]4 (1: M = Co; 2: M =
Ni), where HL·S represents a pyridyl-alcohol-type ligand
with a thioether functional group, introduced to allow
subsequent binding to Au surfaces. Dc and ac magnetic
susceptibility data of 1 and 2 were modeled with a full spin
Hamiltonian implemented in the computational framework
CONDON 2.0. Although both coordination clusters 1 and 2 are
isostructural, with each of their transition metal ions in a
pseudo-octahedral coordination environment of four Cl atoms
and N,O-donor atoms of one chelating HL·S ligand, the
substantially different ligand field effects of Co(II) and
Ni(II) results in stark differences in their magnetism. In
contrast to compound 1 which exhibits a dominant
antiferromagnetic intramolecular coupling (J = −0.14
cm−1), 2 is characterised by a ferromagnetic coupling (J =
+10.6 cm−1) and is considered to be a single-molecule
magnet (SMM), a feature of special interest for future
surface deposition studies. An analysis based on density
functional theory (DFT) was performed to explore possible
magnetostructural correlations in these compounds. Using a
two-J model Hamiltonian, it revealed that compound 1 has
four positive and two (small) negative JCoCo isotropic
interactions leading to a SHS = 6 ground state. Taking into
account the magnetic anisotropy, one would recover a MS = 0
ground state since D > 0 from computations. In 2, all the J
constants are positive and, in this framework, the
zero-field splitting energy characterising the axial
anisotropy was estimated to be negative (D = −0.44
cm−1). The computational results are consistent with
compound 2 being an SMM.},
cin = {PGI-6},
ddc = {540},
cid = {I:(DE-Juel1)PGI-6-20110106},
pnm = {422 - Spin-based and quantum information (POF2-422)},
pid = {G:(DE-HGF)POF2-422},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000335926800025},
pubmed = {pmid:24705925},
doi = {10.1039/c4dt00306c},
url = {https://juser.fz-juelich.de/record/201881},
}