A Convenient DFT-Based Strategy for Predicting Transition Temperatures of Valence Tautomeric Molecular Switches

Jett T Janetzki; F Zahra M Zahir; Robert W Gable; Wasinee Phonsri; Keith S Murray; Lars Goerigk; Colette Boskovic

Journal article

A Convenient DFT-Based Strategy for Predicting Transition Temperatures of Valence Tautomeric Molecular Switches

Jett T Janetzki, F Zahra M Zahir, Robert W Gable, Wasinee Phonsri, Keith S Murray, Lars Goerigk, Colette Boskovic

INORGANIC CHEMISTRY | AMER CHEMICAL SOC | Published : 2021

DOI: 10.1021/acs.inorgchem.1c02273

Abstract

The ability to identify promising candidate switchable molecules computationally, prior to synthesis, represents a considerable advance in the development of switchable molecular materials. Even more useful would be the possibility of predicting the switching temperature. Cobalt-dioxolene complexes can exhibit thermally induced valence tautomeric switching between low-spin CoIII-catecholate and high-spin CoII-semiquinonate forms, where the half-temperature (T1/2) is the temperature at which there are equal amounts of the two tautomers. We report the first simple computational strategy for accurately predicting T1/2 values for valence tautomeric complexes. Dispersion-corrected density functio..

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University of Melbourne Researchers

Lars Goerigk Author Chemistry

Robert Gable Author Chemistry

Colette Boskovic Author Chemistry

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Grants

Awarded by Australian Research Council

Awarded by National Computational Merit Allocation Scheme

Awarded by Research Platform Services (ResPlat) at The University of Melbourne

Awarded by sustaining and strengthening meritbased access to the NCI LIEF Grant

Funding Acknowledgements

C.B. thanks the Australian Research Council for financial support (DP190100854). L. G. is grateful for generous allocations of computational resources from the National Computational Infrastructure (NCI) Facility within the National Computational Merit Allocation Scheme (project fk5) and Research Platform Services (ResPlat) at The University of Melbourne (project punim0094). This research was also supported by the sustaining and strengthening meritbased access to the NCI LIEF Grant (LE190100021) facilitated by The University of Melbourne. KSM thanks the Australian Research Council for support (DP170100034). This research was undertaken in part using the MX2 beamline at the Australian Synchrotron, part of ANSTO, and made use of the ACRF detector.