2020
DOI: 10.1039/d0cp00438c
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Ultrafast dynamics in LMCT and intraconfigurational excited states in hexahaloiridates(iv), models for heavy transition metal complexes and building blocks of quantum correlated materials

Abstract: The population and structural dynamics of IrCl62- is studied in acetonitrile and aqueous solutions in comparison to isoelectronic IrBr62- using ultrafast broadband, dispersed transient absorption, with both octahedra excited with...

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Cited by 12 publications
(4 citation statements)
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“…Because the LMCT contribution in the case of 385 nm excited BiBr 6 3– is less significant than in the case of the 530 nm excited BiI 6 3– , ,,,,, the long-lived Δ A signal can be assigned to the population of the metastable (> 2 ns) 3 A 1u excited state. Lifetimes of low-energy excited electronic states of predominantly metal-centered character in complexes of heavy metal ions, such as, e.g., Ir 4+ , can be in a nanosecond range in room-temperature solutions when these states are not strongly vibronically coupled to the ligand environment, which is the case of halide ligands.…”
Section: Discussionmentioning
confidence: 99%
“…Because the LMCT contribution in the case of 385 nm excited BiBr 6 3– is less significant than in the case of the 530 nm excited BiI 6 3– , ,,,,, the long-lived Δ A signal can be assigned to the population of the metastable (> 2 ns) 3 A 1u excited state. Lifetimes of low-energy excited electronic states of predominantly metal-centered character in complexes of heavy metal ions, such as, e.g., Ir 4+ , can be in a nanosecond range in room-temperature solutions when these states are not strongly vibronically coupled to the ligand environment, which is the case of halide ligands.…”
Section: Discussionmentioning
confidence: 99%
“…[25][26][27] Similarly, p donating bromide ligands facilitate two sets of LMCT transitions in [IrBr 6 ] 2− , one in the visible (ranging from 500 to 900 nm) attributed to population of the t * 2g orbital and a second in the UV (spanning 250 nm to 450 nm) attributed to population of the e * g orbital. [28][29][30] While a large number of coordination complexes exhibit LMCT transitions, very few undergo excited state reactivity from their LMCT excited state, and thus only a handful have been employed as photosensitizers or photocatalysts. When identifying coordination complexes with LMCT excited states for photochemical applications, there are several considerations.…”
Section: Designing Transition Metal Complexes With Low-lying Lmct Exc...mentioning
confidence: 99%
“…25–27 Similarly, π donating bromide ligands facilitate two sets of LMCT transitions in [IrBr 6 ] 2− , one in the visible (ranging from 500 to 900 nm) attributed to population of the orbital and a second in the UV (spanning 250 nm to 450 nm) attributed to population of the orbital. 28–30…”
Section: Designing Transition Metal Complexes With Low-lying Lmct Exc...mentioning
confidence: 99%
“…This initial electron relaxation (hot electron cooling) is fast due to strong NA couplings associated with metal-involved vibrational modes. Recent studies of nonradiative relaxation dynamics in IrBr 6 2– and IrCl 6 2– by means of ultrafast broadband transient absorption spectroscopy have shown a similar fast 100–400 fs transition from the initially excited LMCT state(s) to the metal-center (MC) state, rationalized by the Jahn–Teller effect. …”
mentioning
confidence: 97%