%0 Journal Article
%A Velazquez Garcia, Jose
%A Basuroy, Krishnayan
%A Storozhuk, Darina
%A Wong, Joanne
%A Demeshko, Serhiy
%A Meyer, Franc
%A Henning, Robert
%A Techert, Simone
%T Short- vs Long-range Elastic Distortion: Structural Dynamics of a [2x2] Tetrairon(II) Spin Crossover Grid Complex Observed by Time-Resolved X-Ray Crystallography
%J Dalton transactions
%V 51
%N 46
%@ 0300-9246
%C London
%I Soc.
%M PUBDB-2022-05040
%P 17558 - 17566
%D 2022
%X 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-bis6-(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.
%F PUB:(DE-HGF)16
%9 Journal Article
%$ pmid:36315244
%U <Go to ISI:>//WOS:000877125300001
%R 10.1039/d2dt02638d
%U https://bib-pubdb1.desy.de/record/482965