Time resolved structural studies in molecular materials

Jarzembska, Katarzyna N.; Kamiński, Radosław

doi:10.1016/b978-0-12-823144-9.00107-2

Comprehensive Inorganic Chemistry III 2023

DOI: 10.1016/b978-0-12-823144-9.00107-2

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Time resolved structural studies in molecular materials

Katarzyna N. Jarzembska

Radosław Kamiński²

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2024

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Cited by 3 publications

References 180 publications

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

Borowski

Jarzembska

Kamiński

et al. 2023

Crystal Growth & Design

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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.

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

Borowski

Jarzembska

Kamiński

et al. 2023

Crystal Growth & Design

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Nanosecond-Lived Excimer Observation in a Crystal of a Rhodium(I) Complex via Time-Resolved X-ray Laue Diffraction

Łaski,

Bosman,

Drapała

et al. 2024

J. Phys. Chem. Lett.

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The rare observation of transient Rh•••Rh excimer formation in a single crystal is reported. The estimated excited-state lifetime at 100 K is 2 ns, which makes it the shortest-lived small-molecule species caught experimentally using the laser-pump/ X-ray-probe time-resolved Laue method. Upon excitation with 390 nm laser light, the intermolecular Rh•••Rh distance decreases from 3.379(4) to 3.19(1) Å, and the metal− metal contact gains more bonding character. On the basis of the experimental results and theoretical modeling, the structural changes determined with 100 ps time resolution reflect principally the S 0 → S 1 electronic transition.

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Photocrystallography – common or exclusive?

Jarzembska

2024

Acta Crystallogr C Struct Chem

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Time resolved structural studies in molecular materials

Cited by 3 publications

References 180 publications

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

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

Nanosecond-Lived Excimer Observation in a Crystal of a Rhodium(I) Complex via Time-Resolved X-ray Laue Diffraction

Photocrystallography – common or exclusive?

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