Harnessing high-energy MLCT excited states for artificial photosynthesis

Cotic, Agustina; Ramírez-Wierzbicki, Ivana; Cadranel, Alejandro

doi:10.1016/j.ccr.2024.215878

Cited by 2 publications

(1 citation statement)

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“…The ability to manipulate IC depends on its physical origin, and with it, on the electronic configuration of the initial and final states and on the energy profile of the IC reaction coordinate. In MLCT chromophores, [11] hole reconfiguration (HR) is an IC process involving a change in the excited hole configuration within the metal ion, with a fixed configuration of the excited electron within an acceptor ligand. For example, chromophore [Ru(tpm)(bpy)(NCS)] + (1 in Figure 1), where tpm is tris(1-pyrazolyl)methane and bpy is 2,2'-bipyridine, is a model for HR, which can be described using the MO diagram in Figure 1 and the excited states that evolve from it.…”

Section: Introductionmentioning

confidence: 99%

Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores

Cotic,

Heinemann,

Slep

et al. 2024

ChemPhysChem

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In MLCT chromophores, internal conversion (IC) in the form of hole reconfiguration pathways (HR) is a major source of dissipation of the absorbed photon energy. Therefore, it is desirable to minimize their impact in energy conversion schemes by slowing them down. According to previous findings on {Ru(bpy)} chromophores, donor‐acceptor interactions between the Ru ion and the ligand scaffold might allow to control HR/IC rates. Here, a series of [Ru(tpm)(bpy)(R‐py)]2+ chromophores, where tpm is tris(1‐pyrazolyl)methane, bpy is 2,2’‐bipyridine and R‐py is a 4‐substituted pyridine, were prepared and fully characterized employing electrochemistry, spectroelectrochemistry, steady‐state absorption/emission spectroscopy and electronic structure computations based on DFT/TD‐DFT. Their excited‐state decay was monitored using nanosecond and femtosecond transient absorption spectroscopy. HR/IC lifetimes as slow as 568 ps were obtained in DMSO at room temperature, twice as slow as in the reference species [Ru(tpm)(bpy)(NCS)]+.

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Section: Introductionmentioning

confidence: 99%