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Modulation of the carboxamidine redox potential through photoinduced spiropyran or fulgimide isomerisation

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Abstract

Carboxamidines functionalized with either a spiropyran or fulgimide photoswitch were prepared on multigram scales. The thermal, electrochemical, and photochemical ring isomerizations of these compounds were studied and the results compared with related systems. The photochemical isomerisations were found to be reversible and could be followed by 1H NMR and UV-vis spectroscopy. The spiropyran/merocyanine couple was thermally active and an activation enthalpy of 116 kJ mol−1 was measured for ring-opening. These measurements yielded an enthalpy difference of 25 kJ mol−1 between the open and closed states which is consistent with DFT calculations. DFT calculations predicted a charge transfer to the carboxamidine group upon ring closure in the fulgimide and a charge transfer from the carboxamidine group upon switching the spiropyran to the merocyanine form. This was confirmed experimentally by monitoring the change in the oxidation potential assigned to the carboxamidine group. The potential of these molecules to therefore act as a new class of photoresponsive ligands that can modulate the ligand field of a complex is discussed.

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Acknowledgements

We are grateful for financial support from the Robert A. Welch Foundation (D-1838, USA), Texas Tech University and from the National Science Foundation (NMR instrument grant CHE-1048553). The authors would like to thank Dr Daniel Unruh and the Texas Tech University X-ray Facility for the crystallographic information discussed herein.

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  1. Ping Peng

    Present address: Current address: State Key Laboratory of Materials Processing and Die & Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan, 730074, P. R. China

  2. Amit Rajput

    Present address: Current address: Department of Basic and Applied Science, School of Engineering, G.D. Goenka University, Sohna Road, Gurgaon, 122103, Haryana, India

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  1. Department of Chemistry and Biochemistry, Texas Tech University, MS 41061, Lubbock, TX, 79409, USA

    M. Crawford Andrews, Ping Peng, Amit Rajput & Anthony F. Cozzolino

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Andrews, M.C., Peng, P., Rajput, A. et al. Modulation of the carboxamidine redox potential through photoinduced spiropyran or fulgimide isomerisation. Photochem Photobiol Sci 17, 432–441 (2018). https://doi.org/10.1039/c7pp00347a

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