A Modular Approach to Light Capture and Synthetic Tuning of the Excited-State Properties of Fe(II)-Based Chromophores.

Abstract

The development of chromophores based on earth-abundant transition metals whose photophysical properties are dominated by their charge-transfer excited states has inspired considerable research over the past decade. One challenge associated with this effort is satisfying the dual requirements of a strong ligand field and chemical tunability of the compound's absorptive cross-section. Herein we explore one possible approach using a heteroleptic compositional motif that combines both of these attributes into a single compound. With the parent complex [Fe(phen)3]2+ (1; where phen is 1,10-phenanthroline) as the starting material, replacement of one of the phen ligands for two cyanides to obtain Fe(phen)2(CN)2 (2) allows for conversion to [Fe(phen)2(C4H10N4)]2+ (3), a six-coordinate Fe(II) complex whose coordination sphere consists of two chelating polypyridyl ligands and one bidentate carbene-based donor. Ground-state absorption spectra of all three compounds exhibit 1A1 → 1MLCT transition(s) associated with the phen ligands that are relatively insensitive to the identity of the third counterligand(s). Ultrafast time-resolved electronic absorption measurements revealed lifetimes for the MLCT excited states of compounds 1 and 2 of 180 ± 30 and 250 ± 90 fs, respectively, values that are typical for iron(II)-based polypyridyl complexes. The corresponding kinetics for compound 3 were substantially slower at 7.4 ± 0.9 ps; the spectral evolution associated with these dynamics confirms that these kinetics are tracking the MLCT excited state and, more importantly, are coupled to ground-state recovery from this excited state. The data are interpreted in terms of a modulation of the relative energies of the MLCT and ligand-field states across the series, leading to a systematic destabilization of metal-localized ligand-field excited states such that the low-energy portions of the charge-transfer and ligand-field manifolds are at or near an energetic inversion point in compound 3. We believe these results illustrate the potential for a modular, orthogonal approach to chromophore design in which part of the coordination sphere can be targeted for light absorption while another can be used to tune electronic-state energetics.