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@PHDTHESIS{Baranowski:1032293,
author = {Baranowski, Daniel},
title = {{P}robing the {T}ransformation from {T}ransition {M}etal
{C}omplexes to {E}xtended {T}wo-{D}imensional
{N}anostructures},
volume = {284},
school = {Duisburg-Essen},
type = {Dissertation},
address = {Jülich},
publisher = {Forschungszentrum Jülich GmbH Zentralbibliothek, Verlag},
reportid = {FZJ-2024-06132},
isbn = {978-3-95806-772-1},
series = {Reihe Schlüsseltechnologien / Key Technologies},
pages = {XII, 103},
year = {2024},
note = {Dissertation, Duisburg-Essen, 2024},
abstract = {The controlled on-surface stabilization of functional
transition metal centers can be realized by embedding them
in a coordination environment of an organic backbone. Then,
realizing twodimensional materials with improved stability
and novel properties is possible through the careful design
of the organic backbone. An understanding of the changes
induced by the transition from isolated transition
metal-organic complexes to their extended structures has
been defined as the subject of this work. Thereby,
transition metal-containing covalent networks and
metal-organic frameworks have been realized. Starting from
nickel tetraphenylporphyrin polymers, the emergence of
π-delocalization in the molecular backbone as a consequence
of polymerization has been confirmed by the appearance of
energy-dispersive electronic valence states. This is quite
surprising since the polymers have been determined to be
amorphous by scanning tunneling microscopy measurements.
Simultaneously, a defined functionality of the nickel
centers has been observed during spectroscopic
characterization. The two-dimensional nickel-containing
polymers can be tuned by the reactivity of the surface used
for their stabilization. Though indicated by the results
obtained via theoretical modeling, the energy-dispersive
nature of the nickel 3d-based valence states has turned out
as experimentally not accessible. To mimic the functional
center of nickel tetraphenylporphyrin, the transition from
nickel 1,2,4,5-tetracyanobenzene complexes to
two-dimensional metal-organic framework has been realized.
Thereby, the energy level alignment can be adjusted to
enable experimental access to the nickel 3dbased valence
states. The appearance of π-conjugation for the nickel
3d-based valence states upon formation of the polymeric
structure has been clearly confirmed following the same
multi-technique approach applied for the characterization of
covalent nickel tetraphenylporphyrin networks.},
cin = {PGI-6},
cid = {I:(DE-Juel1)PGI-6-20110106},
pnm = {5211 - Topological Matter (POF4-521)},
pid = {G:(DE-HGF)POF4-5211},
typ = {PUB:(DE-HGF)3 / PUB:(DE-HGF)11},
doi = {10.34734/FZJ-2024-06132},
url = {https://juser.fz-juelich.de/record/1032293},
}