Journal Article

PUBDB-2022-05040

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Short- vs Long-range Elastic Distortion: Structural Dynamics of a [2x2] Tetrairon(II) Spin Crossover Grid Complex Observed by Time-Resolved X-Ray Crystallography

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*

2022
Soc. London

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Please use a persistent id in citations: doi:10.1039/d2dt02638d  doi:10.3204/PUBDB-2022-05040

Abstract: Spin crossover complexes (SCO) are among the most studied molecular switches due to their potential use in displays, sensors, actuators and memory components. A prerequisite to using these materials is the understanding of the structural changes following the spin transition at out-of-equilibrium conditions. So far, out-of-equilibrium studies in SCO solids have been focused on mononuclear complexes, though a growing number of oligonuclear SCO complexes showing cooperative effects are being reported. Here, we use time-resolved pink Laue crystallography to study the out-of-equilibrium dynamics of a [2 × 2] tetranuclear metallogrid of the form [Fe II4 LMe4](BF4)4·2MeCN ([LMe]− = 4-methyl-3,5-bis{6-(2,2′-bipyridyl)}pyrazolate). The out-of-equilibrium spin state switching induced by a ps laser pulse demonstrates that the metallogrid exhibits a multi-step response similar to that reported for mononuclear complexes. Contrary to the mononuclear complexes, the metallogrid shows two types of elastic distortions at different time scales. The first is a short-range distortion that propagates over the entire Fe4 grid complex during the ps time scale, and it is caused by the rearrangement of the coordination sphere of the photo-switching ion and the constant feedback between strongly linked metal ions. The second is a long-range distortion caused by the anisotropic expansion of the lattice during the ns time scale, observed in mononuclear materials. The structural analysis demonstrates that the long-range prevails over the short-range distortion, inducing the largest deformation of both the entire grid and the coordination sphere of each metal ion. The present study sheds light on the out-of -equilibrium dynamics of a non-cooperative oligonuclear complex.

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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 C02 - In-situ hochauflösende Untersuchung des aktiven Zustands bei der (photo-) elektrochemischen Wasserspaltung (C02) (240172646) (240172646)
4. SFB 1073 B06 - Echtzeituntersuchungen der optischen Anregung in oligonuklearen Metallkomplexen mit schaltbaren Spin- und Ladungszuständen (B06) (240171831) (240171831)

Experiment(s):

1. Measurement at external facility
2. PETRA Beamline P11 (PETRA III)

Appears in the scientific report 2022

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Database coverage:
; ; ; Allianz-Lizenz / DFG ; 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 ; Nationallizenz ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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