Structural Capture of η<sup>1</sup>-OSO to η<sup>2</sup>-(OS)O Coordination Isomerism in a New Ruthenium-Based SO<sub>2</sub>-Linkage Photoisomer That Exhibits Single-Crystal Optical Actuation.
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Cole, J. M., Gosztola, D. J., & Velazquez-Garcia, J. d. J. (2022). Structural Capture of η<sup>1</sup>-OSO to η<sup>2</sup>-(OS)O Coordination Isomerism in a New Ruthenium-Based SO<sub>2</sub>-Linkage Photoisomer That Exhibits Single-Crystal Optical Actuation.. https://doi.org/10.1021/acs.jpcc.2c00170
Funder: Royal Commission for the Exhibition of 1851
Funder: Science and Technology Facilities Council
Recent discoveries of a range of single-crystal optical actuators are feeding a new form of materials chemistry, given their broad range of potential applications, from light-induced molecular motors to light sensors and optical-memory media. A series of ruthenium-based coordination complexes that exhibit sulfur dioxide linkage photoisomerization is of particular interest because they exhibit single-crystal optical actuation via either optical switching or nano-optomechanical transduction processes. We report the discovery of a new complex in this series of chemicals, [Ru(SO<sub>2</sub>)(NH<sub>3</sub>)<sub>4</sub>(3-fluoropyridine)]tosylate<sub>2</sub> (<b>1</b>), which forms an η<sup>1</sup>-OSO photoisomer with 70% photoconversion upon the application of 505 nm light. The uncoordinated oxygen atom in this η<sup>1</sup>-OSO photoisomer impinges on one of the arene rings in a neighboring tosylate counter ion of <b>1</b> just enough that incipient nano-optomechanical transduction is observed. The structure and optical properties of this actuator are characterized via <i>in situ</i> light-induced single-crystal X-ray diffraction (photocrystallography), single-crystal optical absorption spectroscopy and microscopy, as well as single-crystal Raman spectroscopy. These materials-characterization methods were also used to track thermally induced reverse isomerization processes in <b>1</b>. One of these processes involves an η<sup>1</sup>-OSO to η<sup>2</sup>-(OS)O transition, which was found to proceed sufficiently slowly at 110 K that its structural mechanism could be determined via a time sequence of photocrystallography experiments. The resulting data allowed us to structurally capture the transition, which was shown to occur via a form of coordination isomerism. Our newfound knowledge about this structural mechanism will aid the molecular design of new [RuSO<sub>2</sub>] complexes with functional applications.
Consejo Nacional de Ciencia y Tecnolog?a (217553)
Royal Academy of Engineering (RCSRF1819\7\10)
Basic Energy Sciences (DE-AC02-06CH11357)
Cambridge Trust (217553)
External DOI: https://doi.org/10.1021/acs.jpcc.2c00170
This record's URL: https://www.repository.cam.ac.uk/handle/1810/338190
Attribution 4.0 International
Licence URL: https://creativecommons.org/licenses/by/4.0/