Issue 26, 2023

Bidirectional photoswitchability in an iron(iii) spin crossover complex: symmetry-breaking and solvent effects

Abstract

The impact of solvent on spin crossover (SCO) behaviour is reported in two solvates [Fe(qsal-I)2]NO3·2ROH (qsal-I = 4-iodo-2-[(8-quinolylimino)methyl]phenolate; R = Me 1 or Et 2) which undergo abrupt and gradual SCO, respectively. A symmetry-breaking phase transition due to spin-state ordering from a [HS] to [HS-LS] state occurs at 210 K in 1, while T1/2 = 250 K for the EtOH solvate, where complete SCO occurs. The MeOH solvate exhibits LIESST and reverse-LIESST from the [HS-LS] state, revealing a hidden [LS] state. Moreover, photocrystallographic studies on 1 at 10 K reveal re-entrant photoinduced phase transitions to a high symmetry [HS] phase when irradiated at 980 nm or a high symmetry [LS] phase after irradiation at 660 nm. This study represents the first example of bidirectional photoswitchability and subsequent symmetry-breaking from a [HS-LS] state in an iron(III) SCO material.

Graphical abstract: Bidirectional photoswitchability in an iron(iii) spin crossover complex: symmetry-breaking and solvent effects

Supplementary files

Article information

Article type
Edge Article
Submitted
22 mar 2023
Accepted
31 may 2023
First published
01 iyn 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 7185-7191

Bidirectional photoswitchability in an iron(III) spin crossover complex: symmetry-breaking and solvent effects

R. Díaz-Torres, G. Chastanet, E. Collet, E. Trzop, P. Harding and D. J. Harding, Chem. Sci., 2023, 14, 7185 DOI: 10.1039/D3SC01495A

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