Spectroscopic Study of theE/ZPhotoisomerization of a New Cyrhetrenyl Acylhydrazone: A Potential Photoswitch and Photosensitizer(dagger): A Potential Photoswitch and Photosensitizer

Patricia M. Toro, Danilo H. Jara, A. Hugo Klahn, David Villaman, Mauricio Fuentealba, Andrés Vega, Nancy Pizarro

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

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Resumen

The new cyrhetrenyl acylhydrazone [(CO)3Re(η5-C5H4)-C(O)-NH-N = C(CH3)-(2-C4H2S-5-NO2)] (E-CyAH) has been designed, synthesized and fully characterized to study the effect of having a cyrhetrenyl fragment (sensitizer) covalently bonded to an acylhydrazone moiety (switch), on its photophysical and photochemical properties. The crystal structure reveals that E-CyAH adopts an E-configuration around the iminic moiety [-N = C(CH3)]. The absorption spectrum of E-CyAH displays two bands at 270 and 380 nm, which are mainly ascribed to π → π* intraligand (IL) and dπ → π* metal-to-ligand charge transfer (MLCT) transitions, being consistent with DFT/TD-DFT calculations. Upon 365 nm irradiation, E-CyAH photoisomerizes to Z-CyAH, as evidenced by UV-Vis and 1H-NMR spectral changes, with a quantum yield value ΦE-CyAH →Z-CyAH of 0.30. Z-CyAH undergoes a first-order thermal back-isomerization process, with a relatively short half-life τ1/2 of 277 min. Consequently, E-CyAH was quantitatively recovered after 24 h, making it a fully reversible T-type molecular photoswitch. This remarkable behavior allows us to measure the individual photophysical properties for both isomers. In addition, E-CyAH and Z-CyAH efficiently photosensitize the generation of singlet oxygen (O2 (1Δg)) with good yield (ΦΔ = 0.342).

Idioma originalInglés
PublicaciónPhotochemistry and Photobiology
DOI
EstadoPublicada - 28 jul 2020

Áreas temáticas de ASJC Scopus

  • Bioquímica
  • Química física y teórica
  • Radiación

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