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Updated: Jun 29, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Control of Photoisomerization Kinetics via Multistage Switching in Bimetallic Ru(II)-Terpyridine Complexes
Soumi Das1, Manoranjan Bar1, Tanusree Ganguly1
1Department of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata 700032, India.
Abstract:
In this study, we carried out detailed experimental and theoretical investigation on photophysical, electrochemical, and photoisomerization behaviors of a new array of luminescent binuclear Ru(II) complexes derived from a phenylene-vinylene-substituted terpyridyl ligand possessing RT lifetimes within 60.3-410.5 ns. The complexes experienced trans-to-cis isomerization in MeCN on irradiation with visible light, accompanied by significant changes in their absorption and emission spectral profiles. The reverse cis-to-trans process is also possible with the use of ultraviolet (UV) light. On conversion from trans to cis isomers, the emission intensity increases substantially, while for the reverse process, luminescence quenching occurs. Thus, "off-on" and "on-off" emission switching is facilitated upon treatment with visible and UV light alternatively. By the use of chemical oxidants (ceric ammonium nitrate and potassium permanganate) and reductants (metallic sodium) as well as light of appropriate wavelengths, multistate switching phenomena involving reversible oxidation-reduction and trans-cis isomerization have been achieved. Interestingly, the rate of this multistate photoswitching process becomes much faster compared to only two-state trans-cis isomerization of these complexes. Density functional theory (DFT) and time-dependent-DFT (TD-DFT) calculations are also performed to obtain a clear picture of the electronic environment of the complexes and also for the appropriate assignment of absorption and emission spectral bands.
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