Low-energy optical switching of SO<sub>2</sub> linkage isomerisation in single crystals of a ruthenium-based coordination complex.
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Cole, J. M., Gosztola, D. J., & Sylvester, S. O. (2021). Low-energy optical switching of SO<sub>2</sub> linkage isomerisation in single crystals of a ruthenium-based coordination complex.. RSC advances, 11 (22), 13183-13192. https://doi.org/10.1039/d1ra01696b
Single crystals that behave as optical switches are desirable for a wide range of applications, from optical sensors to read-write memory media. A series of ruthenium-based complexes that exhibit optical switching in their single-crystal form <i>via</i> SO<sub>2</sub> linkage photoisomerisation are of prospective interest for these technologies. This study explores the optical switching behaviour in one such complex, <i>trans</i>-[Ru(SO<sub>2</sub>)(NH<sub>3</sub>)<sub>4</sub>(H<sub>2</sub>O)]tosylate<sub>2</sub> (1), in terms of its dark and photoinduced crystal structure, as well as its light and thermal decay characteristics, which are deduced by photocrystallography, single-crystal optical absorption spectroscopy and microscopy. Photocrystallography results reveal that a photoisomerisation level of 21.5(5)% is achievable in 1. Biphasic photochromic crystals of 1 were generated by applying green and then red light to switch on and off the η<sup>2</sup>-(OS)O photoisomer in different regions of a crystal. Heat is a known alternative to its thermal decay, whereby a method is demonstrated that employs optical absorption spectra to determine its activation energy of 30 kJ mol<sup>-1</sup>. This low-energy barrier to optical switching agrees well with computational studies on 1, as well as being comparable to activation energies in ruthenium-based nitrosyl linkage photoisomers that also display solid-state optical switching.
Royal Academy of Engineering (RCSRF1819\7\10)
Cambridge Commonwealth Trust (PhD Scholarship (for Sven Sylvester))
Science and Technology Facilities Council (Fellowship support via the ISIS Neutron and Muon F)
Basic Energy Sciences (DE-AC02-06CH11357)
External DOI: https://doi.org/10.1039/d1ra01696b
This record's URL: https://www.repository.cam.ac.uk/handle/1810/337221
Attribution-NonCommercial 4.0 International
Licence URL: https://creativecommons.org/licenses/by-nc/4.0/