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@ARTICLE{Schmitz:873537,
author = {Schmitz, Sebastian and Qiu, Xinkai and Glöß, Maria and
van Leusen, Jan and Izarova, Natalya V. and Nadeem, Muhammad
Arif and Griebel, Jan and Chiechi, Ryan C. and Kögerler,
Paul and Monakhov, Kirill Yu.},
title = {{C}onductive {S}elf-{A}ssembled {M}onolayers of
{P}aramagnetic {{C}o{IIC}o4{III}} and {{C}o4{IIC}o2{III}}
{C}oordination {C}lusters on {G}old {S}urfaces},
journal = {Frontiers in Chemistry},
volume = {7},
issn = {2296-2646},
address = {Lausanne},
publisher = {Frontiers Media},
reportid = {FZJ-2020-00805},
pages = {681},
year = {2019},
abstract = {Two polynuclear cobalt(II,III) complexes,
[Co5(N3)4(N-n-bda)4(bza·SMe)2] (1) and
[Co6(N3)4(N-n-bda)2(bza·SMe)5(MeOH)4]Cl (2), where
Hbza·SMe = 4-(methylthio)benzoic acid and N-n-H2bda =
N-n-butyldiethanolamine, were synthesized and fully
characterized by various techniques. Compound 1 exhibits an
unusual, approximately C2-symmetric {CoIICoIII4} core of two
isosceles Co3 triangles with perpendicularly oriented
planes, sharing a central, high-spin CoII ion residing in a
distorted tetrahedral coordination environment. This central
CoII ion is connected to four outer, octahedrally
coordinated low-spin CoIII ions via oxo bridges. Compound 2
comprises a semi-circular {CoII4CoIII2} motif of four
non-interacting high-spin CoII and two low-spin CoIII
centers in octahedral coordination environments.
Self-assembled monolayers (SAMs) of 1 and 2 were physisorbed
on template-stripped gold surfaces contacted by an eutectic
gallium-indium (EGaIn) tip. The acquired current
density-voltage (I-V) data revealed that the cobalt-based
SAMs are more electrically robust than those of the
previously reported dinuclear {CuIILnIII} complexes with Ln
= Gd, Tb, Dy, or Y (Schmitz et al., 2018a). In addition,
between 170 and 220°C, the neutral, mixed-valence compound
1 undergoes a redox modification, yielding a {Co5}-based
coordination cluster (1-A) with five non-interacting,
high-spin octahedral CoII centers as indicated by SQUID
magnetometry analysis in combination with X-ray
photoelectron spectroscopy and infrared spectroscopy.
Solvothermal treatment of 1 results in a high-nuclearity
coordination cluster, [Co10(N3)2(N-n-bda)6(bza·SMe)6] (3),
containing 10 virtually non-interacting high-spin CoII
centers.},
cin = {PGI-7 / JARA-FIT / PGI-6},
ddc = {540},
cid = {I:(DE-Juel1)PGI-7-20110106 / $I:(DE-82)080009_20140620$ /
I:(DE-Juel1)PGI-6-20110106},
pnm = {524 - Controlling Collective States (POF3-524)},
pid = {G:(DE-HGF)POF3-524},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:31750287},
UT = {WOS:000502093700001},
doi = {10.3389/fchem.2019.00681},
url = {https://juser.fz-juelich.de/record/873537},
}