Verónica Jornet-Mollá
Interplay between spin crossover and proton migration along short strong hydrogen bonds
Jornet-Mollá, Verónica; Giménez-Saiz, Carlos; Cañadillas-Delgado, Laura; Yufit, Dmitry S.; Howard, Judith A.K.; Romero, Francisco M.
Authors
Carlos Giménez-Saiz
Laura Cañadillas-Delgado
Dr Dmitry Yufit d.s.yufit@durham.ac.uk
Academic Visitor
Judith Howard j.a.k.howard@durham.ac.uk
Emeritus Professor
Francisco M. Romero
Abstract
The iron(II) salt [Fe(bpp)2](isonicNO)2·HisonicNO·5H2O (1) (bpp = 2,6-bis(pyrazol-3-yl)pyridine; isonicNO = isonicotinate N-oxide anion) undergoes a partial spin crossover (SCO) with symmetry breaking at T1 = 167 K to a mixed-spin phase (50% high-spin (HS), 50% low-spin (LS)) that is metastable below T2 = 116 K. Annealing the compound at lower temperatures results in a 100% LS phase that differs from the initial HS phase in the formation of a hydrogen bond (HB) between two water molecules (O4W and O5W) of crystallisation. Neutron crystallography experiments have also evidenced a proton displacement inside a short strong hydrogen bond (SSHB) between two isonicNO anions. Both phenomena can also be detected in the mixed-spin phase. 1 undergoes a light-induced excited-state spin trapping (LIESST) of the 100% HS phase, with breaking of the O4W⋯O5W HB and the onset of proton static disorder in the SSHB, indicating the presence of a light-induced activation energy barrier for proton motion. This excited state shows a stepped relaxation at T1(LIESST) = 68 K and T2(LIESST) = 76 K. Photocrystallography measurements after the first relaxation step reveal a single Fe site with an intermediate geometry, resulting from the random distribution of the HS and LS sites throughout the lattice.
Citation
Jornet-Mollá, V., Giménez-Saiz, C., Cañadillas-Delgado, L., Yufit, D. S., Howard, J. A., & Romero, F. M. (2021). Interplay between spin crossover and proton migration along short strong hydrogen bonds. Chemical Science, 12(3), 1038-1053. https://doi.org/10.1039/d0sc04918b
Journal Article Type | Article |
---|---|
Acceptance Date | Nov 16, 2020 |
Online Publication Date | Nov 16, 2020 |
Publication Date | Jan 21, 2021 |
Deposit Date | Jun 15, 2021 |
Publicly Available Date | Jun 15, 2021 |
Journal | Chemical Science |
Print ISSN | 2041-6520 |
Electronic ISSN | 2041-6539 |
Publisher | Royal Society of Chemistry |
Peer Reviewed | Peer Reviewed |
Volume | 12 |
Issue | 3 |
Pages | 1038-1053 |
DOI | https://doi.org/10.1039/d0sc04918b |
Public URL | https://durham-repository.worktribe.com/output/1241317 |
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Copyright Statement
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence
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