3 years ago

Boosting Vis/NIR Charge-Transfer Absorptions of Iron(II) Complexes by N-Alkylation and N-Deprotonation in the Ligand Backbone

Boosting Vis/NIR Charge-Transfer Absorptions of Iron(II) Complexes by N-Alkylation and N-Deprotonation in the Ligand Backbone
Christian Bissinger, Katja Heinze, Oliver Back, Christoph Förster, Matthias Dorn, Andreas K. C. Mengel
Reversing the metal-to-ligand charge transfer (3MLCT)/metal-centered (3MC) excited state order in iron(II) complexes is a challenging objective, yet would finally result in long-sought luminescent transition-metal complexes with an earth-abundant central ion. One approach to achieve this goal is based on low-energy charge-transfer absorptions in combination with a strong ligand field. Coordinating electron-rich and electron-poor tridentate oligopyridine ligands with large bite angles at iron(II) enables both low-energy MLCT absorption bands around 590 nm and a strong ligand field. Variations of the electron-rich ligand by introducing longer alkyl substituents destabilizes the iron(II) complex towards ligand substitution reactions while hardly affecting the optical properties. On the other hand, N-deprotonation of the ligand backbone is feasible and reversible, yielding deep-green complexes with charge-transfer bands extending into the near-IR region. Time-dependent density functional theory calculations assign these absorption bands to transitions with dipole-allowed ligand-to-ligand charge transfer character. This unique geometric and electronic situation establishes a further regulating screw to increase the energy gap between potentially emitting charge-transfer states and the non-radiative ligand field states of iron(II) dyes. Blue and green iron dyes: N-deprotonation of the ligand backbone of electron-rich polypyridine ligands in push–pull substituted iron(II) complexes yields deep-green complexes with charge-transfer bands extending into the near-IR region. According to theoretical calculations, these absorption bands feature dipole-allowed ligand-to-ligand charge-transfer character (LL′CT).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201700959

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