Structural dynamics of a thermally silent triiron( ii ) spin crossover defect grid complex
2023 | journal article. A publication with affiliation to the University of Göttingen.
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Structural dynamics of a thermally silent triiron( ii ) spin crossover defect grid complex
Velazquez-Garcia, J. de J.; Basuroy, K.; Storozhuk, D.; Wong, J.; Demeshko, S.; Meyer, F. & Henning, R. et al. (2023)
Dalton Transactions, 52(35) pp. 12224-12234. DOI: https://doi.org/10.1039/D3DT02067C
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- Authors
- Velazquez-Garcia, Jose de Jesus; Basuroy, Krishnayan; Storozhuk, Darina; Wong, Joanne; Demeshko, Serhiy; Meyer, Franc; Henning, Robert; Techert, Simone
- Abstract
- A triiron(II) metallogrid was studied upon temperature increase and light irradiation. While lacking thermal spin transition, time-resolved photocrystallography revealed the photoinduced and elastic steps of the out-of-equilibrium dynamics.
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 [2 × 2] triiron( ii ) metallogrid of the form [FeII3L H 2 (HL H ) 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 [2 × 2] 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. - Issue Date
- 2023
- 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
- National Institutes of Health https://doi.org/10.13039/100000002
Deutsche Forschungsgemeinschaft https://doi.org/10.13039/501100001659