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Osmium Complex–Chromophore Conjugates with Both Singlet-to-Triplet Absorption and Long Triplet Lifetime through Tuning of the Heavy-Atom Effect by Yoichi Sasaki; Nobuhiro Yanai; Nobuo Kimizuka is a Chemistry article available to read on EtoBox.

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Os(II) complexes showing singlet-to-triplet absorption are of growing interest as a new class of triplet sensitizers that circumvent energy loss during intersystem crossing, and they enable effective utilization of input photon energy in various applications, such as photoredox catalysis, photodynamic therapy, and photon upconversion. However, triplet excited-state lifetimes of Os(II) complexes are often too short (τ < 1 μs) to transfer their energy to neighboring molecules. While the covalent conjugation of chromophores has been known to extend the net excited-state lifetimes through an intramolecular triplet energy transfer (IMET), heavy-atom effects of the central metals on the attached chromophore units have rarely been discussed. Here, we investigate the relationship between the spin-density contribution of the heavy metals and the net triplet excited-state lifetimes for a series of Os(II) and Ru(II) bis(terpyridine) complexes modified with perylene units. Phosphorescence lifetimes of these compounds strongly depend on the lifetimes of the perylenyl group-localized excited states that are shortened by the heavy-atom effect. The degree of heavy-atom effect can be largely circum

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Author

Yoichi Sasaki; Nobuhiro Yanai; Nobuo Kimizuka

Publisher

American Chemical Society (ACS)

Published

2022

Language

EN

Field

Chemistry (Physical Sciences)