Impact of Cis – Trans Isomerism on Crystal Packing and Photo-Activity of a Cobalt(III) Room-Temperature Photoswitch - Université de Lorraine Access content directly
Journal Articles Crystal Growth & Design Year : 2023

Impact of Cis – Trans Isomerism on Crystal Packing and Photo-Activity of a Cobalt(III) Room-Temperature Photoswitch

Patryk Borowski
Katarzyna Jarzembska
Radosław Kamiński
Krzysztof Durka

Abstract

A bis(acetylacetonato-O,O′)(imidazole)nitrocobalt(III) coordination compound was synthesized and characterized toward photoswitching properties. The compound exists as two isomers, cis and trans, depending on the relative arrangement of the two acetylacetone ligands chelating the metal center. Crystals of both isomers were obtained. The cis form was proven to be photoswitchable in the solid state at room temperature and also to a lesser extent at lower temperatures down to 10 K, upon near-UV irradiation (365–405 nm LED light). Based on the IR spectroscopic results, the photo-reaction is very efficient under ambient conditions with the maximum nitro-to-nitrito conversion reaching ca. 80%. The reaction is reversible. The photo-induced isomer is stable at 100 K, whereas at room temperature, full sample relaxation is observed 7 h after irradiation. Photocrystallographic experiments indicated the formation of the exo-nitrito isomer under continuous illumination of the sample with the 405 nm LED light at room temperature. The achieved conversion amounted to around 60%. In turn, the trans analogue does not exhibit photoswitching properties under such conditions. The experimental solid-state spectroscopic and X-ray diffraction results were supported by theoretical modeling and physicochemical analyses. The differences in photoactivity of the examined cis and trans isomers of the studied compound in the solid state can be explained based on steric and energetic factors.

Dates and versions

hal-04183776 , version 1 (21-08-2023)

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Patryk Borowski, Katarzyna Jarzembska, Radosław Kamiński, Krzysztof Durka, Dominik Schaniel. Impact of Cis – Trans Isomerism on Crystal Packing and Photo-Activity of a Cobalt(III) Room-Temperature Photoswitch. Crystal Growth & Design, 2023, 23 (8), pp.5986-5997. ⟨10.1021/acs.cgd.3c00544⟩. ⟨hal-04183776⟩
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