Journal Article

PUBDB-2023-04837

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Structural Dynamics of a Thermally Silent Triiron(II) Spin Crossover Defect Grid Complex

Velazquez Garcia, J. (Corresponding author)XFEL.EU*DESY* ; Basuroy, K.XFEL.EU*DESY* ; Storozhuk, D.Extern*XFEL.EU* ; Wong, J.Extern* ; Demeshko, S. ; Meyer, F. ; Henning, R. ; Techert, S.XFEL.EU*DESY*

2023
Soc. London

This record in other databases:        

Please use a persistent id in citations: doi:10.1039/D3DT02067C  doi:10.3204/PUBDB-2023-04837

Report No.: DESY-23-115

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.

---

Contributing Institute(s):

1. Strukturdynamik Chemischer Systeme (FS-SCS)

Research Program(s):

1. 633 - Life Sciences – Building Blocks of Life: Structure and Function (POF4-633) (POF4-633)
2. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
3. SFB 1073 B06 - Echtzeituntersuchungen der optischen Anregung in oligonuklearen Metallkomplexen mit schaltbaren Spin- und Ladungszuständen (B06) (240171831) (240171831)
4. SFB 1073 C02 - In-situ hochauflösende Untersuchung des aktiven Zustands bei der (photo-) elektrochemischen Wasserspaltung (C02) (240172646) (240172646)

Experiment(s):

1. PETRA Beamline P11 (PETRA III)

Appears in the scientific report 2023

---

Database coverage:
; ; ; Chemical Reactions ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; Essential Science Indicators ; IF < 5 ; JCR ; National-Konsortium ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

---