Tuning of the antiferromagnetic-type interaction in photo-excited single-decker porphyrin-lanthanide complexes with different crown capping ligands

The magnetic interaction between the total angular momentum (J) of the 4f electrons in a lanthanide ion and the orbital angular momentum (L) of a porphyrin in the photo-excited states of 5,10,15,20-tetraphenylporphyrinato Dy(iii) complexes capped with a crown ether with one of two different symmetries, 12-crown-4 or 1-aza-12-crown-4, was investigated by temperature- and magnetic dependent magnetic circular dichroism (VT-VH MCD). The analysis was conducted on the complexes with different non-aromatic ligands to investigate how different symmetries of the non-aromatic ligands have an impact on the electronic interaction causing an anti-parallel orientation of J and L. The magnitude of the J-L interaction was determined from simulation-based fitting to experimental ratios. While in both cases an antiferromagnetic-type interaction between J and L was identified, an asymmetric non-aromatic ligand resulted in an increased magnitude of the J-L interaction. By using magnetic circular dichroism (MCD), antiferromagnetic-type J-L electronic interaction (Delta JL) in heteroleptic Dy-porphyrin complexes was successfully determined. The Delta JL was tuned by changing the coordinating atoms of the non-aromatic ligands.

Automated summary

The magnetic interaction between the total angular momentum (J) of the 4f electrons in a lanthanide ion and the orbital angular momentum (L) of a porphyrin in the photo-excited states of 5,10,15,20-tetraphenylporphyrinato Dy(iii) complexes capped with a crown ether with one of two different symmetries, 12-crown-4 or 1-aza-12-crown-4, was investigated through temperature- and magnetic dependent magnetic circular dichroism (VT-VH MCD). The analysis revealed that an asymmetric non-aromatic ligand resulted in an increased magnitude of the J-L interaction.