A computational study on the effect of structural isomerism on the excited state lifetime and redox energetics of archetype iridium photoredox catalyst platforms [Ir(ppy)2(bpy)]+ and Ir(ppy)3 DOI
Daniel Alejandro Gomez, Sreeprasad T. Sreenivasan, Balázs Pintér

et al.

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(2)

Published: Jan. 14, 2025

This study investigates the impact of structural isomerism on excited state lifetime and redox energetics heteroleptic [Ir(ppy)2(bpy)]+ homoleptic Ir(ppy)3 photoredox catalysts using ground-state time-dependent density functional theory methods. While ground- excited-state reduction potentials differ only slightly among isomers these complexes, our findings reveal significant variations in radiative non-radiative decay rates reactivity-controlling triplet 3MLCT states closely related species. The observed differences could be traced back to transition dipole moment, vertical energy gaps, spin-orbit coupling isomers. In [Ir(ppy)2(bpy)]+, moment play a role controlling relative states, which we rationalized by vectorial analysis permanent moments ground states. Regarding two Ir(ppy)3, changes were primarily attributed gaps intensity borrowing from other singlet-singlet transitions driven coupling. Non-radiative assessed terms reorganization energies, adiabatic gap, For both energies associated with low-energy molecular vibrations metal-ligand bond length following de-excitation process major contributors. These insights provide deeper understanding how design can leveraged optimize performance iridium-based catalysts, potentially guiding development more efficient catalytic systems for future applications.

Language: Английский

A computational study on the effect of structural isomerism on the excited state lifetime and redox energetics of archetype iridium photoredox catalyst platforms [Ir(ppy)2(bpy)]+ and Ir(ppy)3 DOI
Daniel Alejandro Gomez, Sreeprasad T. Sreenivasan, Balázs Pintér

et al.

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(2)

Published: Jan. 14, 2025

This study investigates the impact of structural isomerism on excited state lifetime and redox energetics heteroleptic [Ir(ppy)2(bpy)]+ homoleptic Ir(ppy)3 photoredox catalysts using ground-state time-dependent density functional theory methods. While ground- excited-state reduction potentials differ only slightly among isomers these complexes, our findings reveal significant variations in radiative non-radiative decay rates reactivity-controlling triplet 3MLCT states closely related species. The observed differences could be traced back to transition dipole moment, vertical energy gaps, spin-orbit coupling isomers. In [Ir(ppy)2(bpy)]+, moment play a role controlling relative states, which we rationalized by vectorial analysis permanent moments ground states. Regarding two Ir(ppy)3, changes were primarily attributed gaps intensity borrowing from other singlet-singlet transitions driven coupling. Non-radiative assessed terms reorganization energies, adiabatic gap, For both energies associated with low-energy molecular vibrations metal-ligand bond length following de-excitation process major contributors. These insights provide deeper understanding how design can leveraged optimize performance iridium-based catalysts, potentially guiding development more efficient catalytic systems for future applications.

Language: Английский

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