Tuning Excited State Electron Transfer in Fe Tetracyano-Polypyridyl Complexes

TL;DR

This study investigates how the excited state electron transfer dynamics in iron polypyridyl complexes can be tuned by solvent and ligand modifications, revealing pathways that influence MLCT lifetimes and the first observation of direct MLCT to ground state relaxation.

Contribution

It demonstrates the first observation of an efficient ^3MLCT to ground state relaxation pathway in an Fe polypyridyl complex and elucidates how ligand structure and solvent affect electron transfer mechanisms.

Findings

^3MLCT lifetimes range from 180 fs to 67 ps depending on solvent.

Non-adiabatic Marcus theory describes the ^3MLCT to ^3MC pathway in complexes 1 and 2.

Direct ^3MLCT to ground state relaxation is significant in complex 3 due to nuclear tunnelling.

Abstract

We have investigated photoinduced intramolecular electron transfer dynamics following metal-to-ligand charge-transfer (MLCT) excitation of [Fe(CN)$_4$(2,2'-bipyridine)]$^{2-}$ (1), [Fe(CN)$_4$(2,3-bis(2-pyridyl)pyrazine)]$^{2-}$ (2) and [Fe(CN)$_4$(2,2'-bipyrimidine)]$^{2-}$ (3) complexes in various solvents with static and time-resolved UV-visible absorption spectroscopy and Fe 2p3d resonant inelastic X-ray scattering. We observe $^3$MLCT lifetimes from 180 fs to 67 ps over a wide range of MLCT energies in different solvents by utilizing the strong solvatochromism of the complexes. Intramolecular electron transfer lifetimes governing $^3$MLCT relaxation increase monotonically and (super)exponentially as the $^3$MLCT energy is decreased in 1 and 2 by changing the solvent. This behavior can be described with non-adiabatic classical Marcus electron transfer dynamics along the indirect $^3$MLCT->$^3$MC pathway, where the $^3$MC is the lowest energy metal-centered (MC) excited state. In contrast, the $^3$MLCT lifetime in 3 changes non-monotonically and exhibits a maximum. This qualitatively different behaviour results from direct electron transfer from the $^3$MLCT to the electronic ground state (GS). This pathway involves nuclear tunnelling for the high-frequency polypyridyl skeleton mode ($\hbar\omega$ = 1530 cm$^{-1}$), which is more displaced for 3 than for either 1 or 2, therefore making the direct pathway significantly more efficient in 3. To our knowledge, this is the first observation of an efficient $^3$MLCT->GS relaxation pathway in an Fe polypyridyl complex. Our study suggests that further extending the MLCT state lifetime requires (1) lowering the $^3$MLCT state energy with respect to the $^3$MC state and (2) suppressing the intramolecular distortion of the electron-accepting ligand in the $^3$MLCT excited state to suppress the rate of direct $^3$MLCT->GS electron transfer.