Structural Capture of η1-OSO to η2-(OS)O Coordination Isomerism in a New Ruthenium-Based SO2-Linkage Photoisomer That Exhibits Single-Crystal Optical Actuation.
View / Open Files
Publication Date
2022-04-07Journal Title
J Phys Chem C Nanomater Interfaces
ISSN
1932-7447
Publisher
American Chemical Society (ACS)
Language
eng
Type
Article
This Version
VoR
Metadata
Show full item recordCitation
Cole, J. M., Gosztola, D. J., & Velazquez-Garcia, J. d. J. (2022). Structural Capture of η1-OSO to η2-(OS)O Coordination Isomerism in a New Ruthenium-Based SO2-Linkage Photoisomer That Exhibits Single-Crystal Optical Actuation.. J Phys Chem C Nanomater Interfaces https://doi.org/10.1021/acs.jpcc.2c00170
Description
Funder: Royal Commission for the Exhibition of 1851
Funder: Science and Technology Facilities Council
Funder: BASF
Abstract
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(SO2)(NH3)4(3-fluoropyridine)]tosylate2 (1), which forms an η1-OSO photoisomer with 70% photoconversion upon the application of 505 nm light. The uncoordinated oxygen atom in this η1-OSO photoisomer impinges on one of the arene rings in a neighboring tosylate counter ion of 1 just enough that incipient nano-optomechanical transduction is observed. The structure and optical properties of this actuator are characterized via in situ 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 1. One of these processes involves an η1-OSO to η2-(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 [RuSO2] complexes with functional applications.
Sponsorship
BASF/Royal Academy of Engineering Research Chair in Data-Driven Molecular Engineering of Functional Materials (part of STFC via the ISIS Neutron and Muon Source); the 1851 Royal Commission of the Great Exhibition (2014 Fellowship in Design); U.S. Department of Energy (DOE) Office of Science, Office of Basic Energy Sciences, and used research resources of the Center for Nanoscale Materials, an Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory, supported by the U.S. DOE, all under contract no. DE-AC02-06CH11357; National Council of Science and Technology of Mexico (CONACyT) and the Cambridge Trust for a PhD Scholarship (217553).
Funder references
STFC (Unknown)
STFC (Unknown)
Identifiers
35573119, PMC9098168
External DOI: https://doi.org/10.1021/acs.jpcc.2c00170
This record's URL: https://www.repository.cam.ac.uk/handle/1810/338190
Statistics
Total file downloads (since January 2020). For more information on metrics see the
IRUS guide.
Recommended or similar items
The current recommendation prototype on the Apollo Repository will be turned off on 03 February 2023. Although the pilot has been fruitful for both parties, the service provider IKVA is focusing on horizon scanning products and so the recommender service can no longer be supported. We recognise the importance of recommender services in supporting research discovery and are evaluating offerings from other service providers. If you would like to offer feedback on this decision please contact us on: support@repository.cam.ac.uk