Insights into the excited state dynamics of Fe(ii) polypyridyl complexes from variable-temperature ultrafast spectroscopy

Abstract

In an effort to better define the nature of the nuclear coordinate associated with excited state dynamics in first-row transition metal-based chromophores, variable-temperature ultrafast time-resolved absorption spectroscopy has been used to determine activation parameters associated with ground state recovery dynamics in a series of low-spin Fe(II) polypyridyl complexes. Our results establish that high-spin (⁵T₂) to low-spin (¹A₁) conversion in complexes of the form [Fe(4,4′-di-R-2,2′-bpy′)₃]²⁺ (R = H, CH₃, or tert-butyl) is characterized by a small but nevertheless non-zero barrier in the range of 300–350 cm⁻¹ in fluid CH₃CN solution, a value that more than doubles to ∼750 cm⁻¹ for [Fe(terpy)₂]²⁺ (terpy = 2,2′:6′,2′′-terpyridine). The data were analyzed in the context of semi-classical Marcus theory. Changes in the ratio of the electronic coupling to reorganization energy (specifically, H_ab⁴/λ) reveal an approximately two-fold difference between the [Fe(bpy′)₃]²⁺ complexes (∼1/30) and [Fe(terpy)₂]²⁺ (∼1/14), suggesting a change in the nature of the nuclear coordinate associated with ground state recovery between these two types of complexes. These experimentally-determined ratios, along with estimates for the ⁵T₂/¹A₁ energy gap, yield electronic coupling values between these two states for the [Fe(bpy′)₃]²⁺ series and [Fe(terpy)₂]²⁺ of 4.3 ± 0.3 cm⁻¹ and 6 ± 1 cm⁻¹, respectively, values that are qualitatively consistent with the second-order nature of high-spin/low-spin coupling in a d⁶ ion. In addition to providing useful quantitative information on these prototypical Fe(II) complexes, these results underscore the utility of variable-temperature spectroscopic measurements for characterizing ultrafast excited state dynamics in this class of compounds.