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@ARTICLE{Monakhov:201879,
author = {Monakhov, Kirill Yu. and López, Xavier and Speldrich,
Manfred and van Leusen, Jan and Kögerler, Paul and
Braunstein, Pierre and Poblet, Josep M.},
title = {{M}agnetochemical {C}omplexity of {H}exa- and
{H}eptanuclear {W}heel {C}omplexes of {L}ate-3d {I}ons
{S}upported by {N},{O}-{D}onor {P}yridyl-{M}ethanolate
{L}igands},
journal = {Chemistry - a European journal},
volume = {20},
number = {13},
issn = {0947-6539},
address = {Weinheim},
publisher = {Wiley-VCH},
reportid = {FZJ-2015-04173},
pages = {3769 - 3781},
year = {2014},
abstract = {The scaffold geometries, stability and magnetic features of
the (pyridine-2-yl)methanolate (L) supported wheel-shaped
transition-metal complexes with compositions [M6L12] (1),
[Na⊂(ML2)6]+ (2), and [M′⊂(ML2)6]2+ (3), in which
M=CoII, NiII, CuII, and ZnII were investigated with density
functional theory (DFT). The goals of this study are
manifold: 1) To advance understanding of the magnetism in
the synthesized compounds [Na⊂(ML2)6]+ and
[M′⊂(ML2)6]2+ that were described in Angew. Chem. Int.
Ed. 2010, 49, 4443 (I-{Na⊂Ni6}, I-{Ni′⊂Ni6}) and
Dalton Trans. 2011, 40, 10526 (II-{Na⊂Co6},
II-{Co′⊂Co6}); 2) To disclose how the structural,
electronic, and magnetic characteristics of 1, 2, and 3
change upon varying MII from d7 (Co2+) to d10 (Zn2+);
3) To estimate the influence of the Na+ and M′2+ ions
(XQ+) occupying the central voids of 2 and 3 on the external
and internal magnetic coupling interactions in these spin
structures; 4) To assess the relative structural and
electrochemical stabilities of 1, 2, and 3. In particular,
we focus here on the net spin polarization, the
determination of the strength and the sign of the exchange
coupling energies, the rationalization of the nature of the
magnetic coupling, and the ground-state structures of 1, 2,
and 3. Our study combines the broken symmetry DFT approach
and the model Hamiltonian methodology implemented in the
computational framework CONDON 2.0 for the modeling of
molecular spin structures, to interpret magnetic
susceptibility measurements of I-{Na⊂Ni6} and
I-{Ni′⊂Ni6}. We illustrate that whereas the structures,
stability and magnetism of 1, 2, and 3 are indeed influenced
by the nature of 3d transition-metals in the {M6} rims, the
XQ+ ions in the inner cavities of 2 and 3 impact these
properties to an even larger degree. As exemplified by
I-{Ni′⊂Ni6}, such heptanuclear complexes exhibit
ground-state multiplets that cannot be described by
simplistic model of spin-up and spin-down metal centers.
Furthermore, we assess how future low-temperature
susceptibility measurements at high magnetic fields can
augment the investigation of compound 3 with M=Co, Ni},
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:000332757100027},
doi = {10.1002/chem.201304177},
url = {https://juser.fz-juelich.de/record/201879},
}