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Hard X-ray-Induced Valence Tautomeric Interconversion in Cobalt-o-Dioxolene Complexes

Francisco, Thiago M., Gee, William J., Shepherd, H.J., Warren, Mark R., Shultz, David A., Raithby, Paul R., Pinheiro, Carlos B. (2017) Hard X-ray-Induced Valence Tautomeric Interconversion in Cobalt-o-Dioxolene Complexes. The Journal of Physical Chemistry Letters, 8 (19). pp. 4774-4778. ISSN 1948-7185. (doi:10.1021/acs.jpclett.7b01794) (KAR id:64721)


Valence tautomeric interconversion (VTI) is a reversible process occurring in metal complexes in which an intramolecular metal–ligand electron transfer is accompanied by a change of metal ion spin state, creating two switchable electronic states (redox isomers). Herein, we describe the low-temperature, 30–100 K, single-crystal study of the [Co(diox)2(4-CN-py)2]·benzene complex (1) (diox = 3,5-di-t-butylsemiquinonate (SQ•-) and/or 3,5-di-t-butylcatecholate (Cat2–) radical; 4-CN-py = 4-cyano-pyridine) using hard synchrotron X-ray radiation with different intensities. We demonstrate for the first time that hard X-rays can induce VTI, and that the interconversion molar fraction is dependent on both intensity and exposure time. This in turn shows that X-rays, as a probe, might be altering the very nature of many structures under investigation at low temperatures, and consequently their properties. Our findings add new perspectives to VTI studies and might be of significant interest to the entire community investigating photoresponsive complexes.

Item Type: Article
DOI/Identification number: 10.1021/acs.jpclett.7b01794
Uncontrolled keywords: Valence tautomeric interconversion, X-ray diffraction, photoresponsive complexes
Subjects: Q Science > QD Chemistry > QD473 Physical properties in relation to structure
Divisions: Divisions > Division of Natural Sciences > Physics and Astronomy
Depositing User: William Gee
Date Deposited: 24 Nov 2017 14:20 UTC
Last Modified: 09 Dec 2022 05:47 UTC
Resource URI: (The current URI for this page, for reference purposes)

University of Kent Author Information

Gee, William J..

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Shepherd, H.J..

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