Remarkable Increase in the Rate of Trans–Cis Photoisomerization of Os(II)-Terpyridine Complexes via Oxidation and Reduction

Luminescent homoleptic Os(II)-terpyridine complexes comprising stilbene-appended naphthalene, anthracene, and pyrene motifs are designed in this work, and their photophysical, electrochemical, and photoisomerization behaviors are extensively investigated. All complexes exhibit intense spin-allowed singlet metal-to-ligand charge transfer (¹MLCT) bands in the visible (496-500 nm) and weaker spin-forbidden singlet-to-triplet ³MLCT transitions in the 600-700 nm range. They display moderate emission at room temperature with lifetimes in the range of 84.5-112.5 ns. Electrochemical studies reveal a reversible Os²⁺/Os³⁺ oxidation couple within 0.93-0.96 V, alongside multiple reversible or quasi-reversible reduction peaks associated with terpyridine units in between -1.10 and -1.85 V. The stilbene motifs facilitate reversible trans-cis photoisomerization under alternative treatment with visible and UV light, enabling the complexes to function as photomolecular switches in the near-infrared domain. Interestingly, a remarkable increase in the rate of photoisomerization has been achieved via oxidation as well as reduction of the complexes, which, in turn, induces multistep switching involving reversible oxidation-reduction and trans-cis isomerization. Computational investigations are also conducted on all three conformations {trans-trans (t-t), trans-cis (t-c), and cis-cis (c-c)} of the complexes to gain insight into their electronic structures and for accurate assignment of their absorption and emission spectral bands.