Room‐Temperature Photogeneration of Nitrosyl Linkage Isomers in Ruthenium Nitrosyl Complexes

• Published in: Chemistry : a European journal Vol. 25; no. 31; pp. 7569 - 7574
• Main Authors: Mikhailov, Artem A., Wenger, Emmanuel, Kostin, Gennadiy A., Schaniel, Dominik
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 04.06.2019; Wiley-VCH Verlag
• Subjects: Chemical Sciences; Chemistry; Cristallography; Data storage; High temperature; Holography; Infrared spectroscopy; Irradiation; Isomerization; Isomers; Material chemistry; nitrosyl; photochemistry; photocrystallography; Pulsed lasers; Room temperature; Ruthenium; Temperature effects; UV/Vis spectroscopy; ruthenium; nitrosyl; photochemistry; UV/Vis spectroscopy; photocrystallography
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201901205

The conditions for the photogeneration of NO linkage isomers at room temperature are studied. By pulsed laser irradiation in the blue spectral range, the long‐lived Ru−ON isomer can be generated at room temperature, which is crucial for potential applications, such as holography and data storage. By using static and time‐resolved spectroscopy (UV/Vis and IR), we give evidence that the liftime of the Ru−(η2‐(NO)) isomer is a decisive parameter for the formation of the Ru−ON isomer at high temperature owing to a two‐step isomerization mechanism Ru−NO→Ru−(η2‐(NO))→Ru−ON. Furthermore, we report the low‐temperature structures for each isomer, which were revealed by photocrystallography. Room‐temperature photoisomerization: The photogeneration of an Ru−ON linkage isomer at room temperature is reported. Combined stationary and time‐resolved spectroscopic methods evidence the two‐step isomerization mechanism: Ru−NO→Ru‐(η2‐(NO))→Ru−ON (see picture). The corresponding molecular structures are obtained by X‐ray diffraction.