Abstract
The new cyrhetrenyl acylhydrazone [(CO)3 Re(η5 -C5 H4 )-C(O)-NH-N=C(CH3 )-(2-C4 H2 S-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 380nm, 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 365nm irradiation, E-CyAH photoisomerizes to Z-CyAH, as evidenced by UV-Vis and 1 H-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 277min. Consequently, E-CyAH was quantitatively recovered after 24h, 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 (1 Δg )) with good yield (ΦΔ =0.342).
Published Version
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