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@ARTICLE{VelazquezGarcia:588610,
author = {Velazquez Garcia, Jose and Basuroy, Krishnayan and
Storozhuk, Darina and Wong, Joanne and Demeshko, Serhiy and
Meyer, Franc and Henning, Robert and Techert, Simone},
title = {{S}tructural {D}ynamics of a {T}hermally {S}ilent
{T}riiron({II}) {S}pin {C}rossover {D}efect {G}rid
{C}omplex},
journal = {Dalton transactions},
volume = {52},
issn = {0300-9246},
address = {London},
publisher = {Soc.},
reportid = {PUBDB-2023-04837, DESY-23-115},
pages = {12224 - 12234},
year = {2023},
abstract = {The structural evolution of spin crossover (SCO) complexes
during their spin transition at equilibrium and
out-of-equilibrium conditions needs to be understood to
enable their successful utilisation in displays, actuators
and memory components. In this study, diffraction techniques
were employed to study the structural changes accompanying
the temperature increase and the light irradiation of a
defect [2x2] triiron (II) metallogrid of the form
[Fe$^{II}$$_3$LH$_2$(HLH)$_2$](BF$_4$)$_4$·4MeCN (FE3),
L$^H$ =3,5-bis{6-(2,2’-bipyridyl)}pyrazole. Although a
multi-temperature crystallographic investigation on single
crystals evidenced that the compound does not exhibit a
thermal spin transition, the structural analysis of the
defect grid suggests that the flexibility of the grid,
provided by a metal-devoid vertex, leads to interesting
characteristics that can be used for intermolecular
cooperativity in related thermally responsive systems.
Time-resolved photocrystallography results reveal that upon
excitation with a ps laser pulse, the defect grid shows the
first two steps of the out-of-equilibrium process, namely
the photoinduced and elastic steps, occurring at the ps and
ns time scales, respectively. Similar to a previously
reported [2x2] tetrairon(II) metallogrid, FE3 exhibits a
local distortion of the entire grid during the photoinduced
step and a long-range distortion of the lattice during the
elastic step. Although the lifetime of the pure photoinduced
high spin (HS) state is longer in the tetranuclear grid than
in the defect grid, suggesting that the global nuclearity
plays a crucial role for the lifetime of the photoinduced
species, the influence of the co-crystalising solvent on the
lifetime of the photoinduced HS state remains unknown. This
study sheds light on the out-of-equilibrium dynamics of a
thermally silent defect triiron SCO metallogrid.},
cin = {FS-SCS},
ddc = {540},
cid = {I:(DE-H253)FS-SCS-20131031},
pnm = {633 - Life Sciences – Building Blocks of Life: Structure
and Function (POF4-633) / 6G3 - PETRA III (DESY) (POF4-6G3)
/ SFB 1073 B06 - Echtzeituntersuchungen der optischen
Anregung in oligonuklearen Metallkomplexen mit schaltbaren
Spin- und Ladungszuständen (B06) (240171831) / SFB 1073 C02
- In-situ hochauflösende Untersuchung des aktiven Zustands
bei der (photo-) elektrochemischen Wasserspaltung (C02)
(240172646)},
pid = {G:(DE-HGF)POF4-633 / G:(DE-HGF)POF4-6G3 /
G:(GEPRIS)240171831 / G:(GEPRIS)240172646},
experiment = {EXP:(DE-H253)P-P11-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:37656445},
UT = {WOS:001059780000001},
doi = {10.1039/D3DT02067C},
url = {https://bib-pubdb1.desy.de/record/588610},
}