Short- vs . long-range elastic distortion: structural dynamics of a [2 × 2] tetrairon( ii ) spin crossover grid complex observed by time-resolved X-Ray crystallography
2022 | journal article. A publication with affiliation to the University of Göttingen.
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Short- vs . long-range elastic distortion: structural dynamics of a [2 × 2] tetrairon( ii ) spin crossover grid complex observed by time-resolved X-Ray crystallography
Velazquez-Garcia, J. de J.; Basuroy, K.; Storozhuk, D.; Wong, J.; Demeshko, S.; Meyer, F. & Henning, R. et al. (2022)
Dalton Transactions, 51(46) pp. 17558-17566. DOI: https://doi.org/10.1039/D2DT02638D
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Details
- Authors
- Velazquez-Garcia, Jose de Jesus; Basuroy, Krishnayan; Storozhuk, Darina; Wong, Joanne; Demeshko, Serhiy; Meyer, Franc; Henning, Robert; Techert, Simone
- Abstract
- Upon irradiation with a ps laser pulse, a [2 × 2] tetrairon(
ii
) spin crossover grid shows two types of elastic distortions: a short-range distortion in ps regime and a long-range distortion in the ns time scale.
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 [FeII4L Me 4 ](BF 4 ) 4 ·2MeCN ([L Me ] − = 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 Fe 4 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. - Issue Date
- 2022
- Journal
- Dalton Transactions
- Project
- SFB 1073: Kontrolle von Energiewandlung auf atomaren Skalen
SFB 1073 | Topical Area B: Umwandlung von optischen Schwingungen
SFB 1073 | Topical Area B | B06 Echtzeituntersuchungen der optischen Anregung in oligonuklearen Metallkomplexen mit schaltbaren Spin- und Ladungszuständen
SFB 1073 | Topical Area C: Photonen- und elektronengetriebene Reaktionen
SFB 1073 | Topical Area C | C02 In situ hochauflösende Untersuchung des aktiven Zustands bei der photo- und elektrochemischen Wasserspaltung - ISSN
- 1477-9226
- eISSN
- 1477-9234
- Language
- English
- Sponsor
- Deutsche Forschungsgemeinschaft https://doi.org/10.13039/501100001659