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@MASTERSTHESIS{Zhou:1042345,
author = {Zhou, Wenling},
title = {{S}pin-{C}rossover in [{F}e({NQ}u3)({NCS})2]: {S}tructural
and {M}agnetic {S}tudies},
school = {RWTH Aachen University},
type = {Masterarbeit},
address = {Jülich},
reportid = {FZJ-2025-02540},
pages = {51 p.},
year = {2025},
note = {Masterarbeit, RWTH Aachen University, 2025},
abstract = {This thesis investigates the magnetic and structural
properties of two batches of single crystals (freshly
synthesized and aged) and polycrystalline material of the
spin-crossover (SCO) compound [Fe(NQu3)(NCS)2]∙0.5 Et2O
(Qu = quinoline and Et = ethyl). Magnetization measurements,
carried out on in-house Superconducting Quantum Interference
Device (SQUID) and on freshly synthesized single crystals,
indicate that the compound exhibits abrupt SCO behaviour
with a hysteresis width of 24.47 K. However, on freshly
synthesized polycrystalline samples and on aged single
crystals, only a paramagnetic signal was obtained across the
entire temperature range (20-300 K) (measured on the Quantum
Design Dynacool-PPMS (Physical Property Measurement
System)), indicating the absence of a SCO. Based on these
observations we believe that the particle size and the
solvent molecules play a critical role in governing the SCO
process.The compound crystallizes in the symmetry C2/c
(measured on in-house SuperNova single-crystal
diffractometer), with the lattice parameters and volume at
room temperature as a = 9.9054(2) Å, b = 22.3828(7) Å, c =
25.8754(8) Å, β = 95.5840(20)°, and V = 5709.63(45) Å3.
For both batches of single crystals, the symmetry was found
to remain unchanged across the entire investigated
temperature range (95-300 K). Based on the electron density
map, the potential positions of the solvent molecules in
freshly synthesized single crystals were identified.
However, the electron density of solvent molecules at the
same positions disappeared in aged single crystals.The fresh
samples show a SCO transition temperature (T1/2) at 138 K in
the cooling process and a temperature of 162.5 K in the
warming process. The lattice parameters a and c, along with
the angle β shrink significantly from HS to LS state, while
the lattice parameter b expands. The FeN6 octahedron
contracts non-uniformly from HS to LS state, in which the
Fe-N bonds are shortened by approximately 0.12 Å to 0.32
Å. Additionally, we observed a gradual increase in
mosaicity when cooling down the crystal.The results on the
fresh crystals are compared and contrasted with the single
crystal diffraction data of the “aged” single crystals,
which do not exhibit a SCO transition, but instead show a
smooth contraction of the unit cell volume with decreasing
temperature. The compound [Fe(NQu3)(NCS)2]∙0.5 Et2O is an
example of a spin crossover compound where the occurrence of
the transition seems to be entirely governed by the
concentration of solvent molecules. This serves as an
excellent entry point for understanding and investigating
the solvent-driven SCO phenomenon.},
cin = {JCNS-2 / JARA-FIT},
cid = {I:(DE-Juel1)JCNS-2-20110106 / $I:(DE-82)080009_20140620$},
pnm = {632 - Materials – Quantum, Complex and Functional
Materials (POF4-632) / 6G4 - Jülich Centre for Neutron
Research (JCNS) (FZJ) (POF4-6G4)},
pid = {G:(DE-HGF)POF4-632 / G:(DE-HGF)POF4-6G4},
typ = {PUB:(DE-HGF)19},
doi = {10.34734/FZJ-2025-02540},
url = {https://juser.fz-juelich.de/record/1042345},
}