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@ARTICLE{Smekhova:877820,
author = {Smekhova, Alevtina and Schmitz, Detlef and Izarova, Natalya
V. and Stuckart, Maria and Shams, S. Fatemeh and
Siemensmeyer, Konrad and de Groot, Frank M. F. and
Kögerler, Paul and Schmitz-Antoniak, Carolin},
title = {{I}ntramolecular crossover from unconventional diamagnetism
to paramagnetism of palladium ions probed by soft {X}-ray
magnetic circular dichroism},
journal = {Communications chemistry},
volume = {3},
number = {1},
issn = {2399-3669},
address = {[London]},
publisher = {Macmillan Publishers Limited, part of Springer Nature},
reportid = {FZJ-2020-02459},
pages = {96},
year = {2020},
abstract = {The case of palladium(II) ions in molecular
polyoxopalladates highlights the importance of accounting
not only for nearest neighbour atoms or ions in order to
understand, model or predict magnetic characteristics. Here,
using site-specific soft X-ray magnetic circular dichroism
(XMCD), the effects of different bond lengths,
delocalization of 4d electrons, and 4d spin-orbit coupling
on the electronic and magnetic properties are investigated
and three different states identified: Conventional
diamagnetism in a square-planar O4 coordination environment,
paramagnetism caused by four additional out-of-plane oxygen
anions, and an unusual diamagnetic state in the
diamagnetic/paramagnetic crossover region modified by
significant mixing of states and facilitated by the
substantial 4d spin-orbit coupling. The two diamagnetic
states can be distinguished by characteristic XMCD fine
structures, thereby overcoming the common limitation of XMCD
to ferro-/ferrimagnetic and paramagnetic materials in
external magnetic fields. The qualitative interpretation of
the results is corroborated by simulations based on charge
transfer multiplet calculations and density functional
theory results.},
cin = {PGI-6},
ddc = {540},
cid = {I:(DE-Juel1)PGI-6-20110106},
pnm = {522 - Controlling Spin-Based Phenomena (POF3-522)},
pid = {G:(DE-HGF)POF3-522},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000555461800001},
doi = {10.1038/s42004-020-0327-9},
url = {https://juser.fz-juelich.de/record/877820},
}