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

Adi, Langit Cahya; Santria, Anas; Ishikawa, Naoto

doi:10.1039/d3dt02842a

Dalton Trans.

2024

DOI: 10.1039/d3dt02842a

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

Langit Cahya Adi,

Anas Santria,

Naoto Ishikawa

Abstract: By using magnetic circular dichroism (MCD), antiferromagnetic-type J–L electronic interaction (ΔJL) in heteroleptic Dy–porphyrin complexes was successfully determined. The ΔJL was tuned by changing the coordinating atoms of the non-aromatic ligands.

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Identification of a Weak Interaction between the Spin-Only 4f-Electronic System of Trivalent Gd Ion and a Photoexcited Cyclic π Electronic System

Santria,

Ishikawa

2024

J. Phys. Chem. A

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An electronic interaction between the spin-only 4felectronic system and the photoexcited π cyclic system has been identified in the anionic bis(phthalocyaninato)gadolinium(III) complex [Pc 2 Gd] − by using variable-temperature variable-magnetic-field magnetic circular dichroism (VTVH MCD). Two positive MCD A-term patterns, corresponding to the Q H and Q L absorption bands, were observed to increase in intensity as the temperature decreased, indicating a ferromagnetic-type interaction between spin angular momentum S of the 4f system and orbital angular momentum L of the photoexcited π system. A theoretical model incorporating the S−L interaction constant C SL was fitted to the VTVH MCD spectra, confirming the presence of a weak interaction, whose intensity was determined as C SL = 0.27 cm −1 for Q L and C SL = 0.02 cm −1 for Q H . Ab initio calculations using the RASSCF and RASSI methods revealed that the inclusion of the excited state calculations with the spin multiplicity (2S + 1) of 6 was crucial for assigning Δ SL and C SL values. This underscores the essential role of the 6 P J term in accurately modeling the S−L interaction in [Pc 2 Gd] − .

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Identification of a Weak Interaction between the Spin-Only 4f-Electronic System of Trivalent Gd Ion and a Photoexcited Cyclic π Electronic System

Santria,

Ishikawa

2024

J. Phys. Chem. A

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show abstract

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

Abstract: By using magnetic circular dichroism (MCD), antiferromagnetic-type J–L electronic interaction (ΔJL) in heteroleptic Dy–porphyrin complexes was successfully determined. The ΔJL was tuned by changing the coordinating atoms of the non-aromatic ligands.

Cited by 1 publication

References 43 publications

Identification of a Weak Interaction between the Spin-Only 4f-Electronic System of Trivalent Gd Ion and a Photoexcited Cyclic π Electronic System

Identification of a Weak Interaction between the Spin-Only 4f-Electronic System of Trivalent Gd Ion and a Photoexcited Cyclic π Electronic System

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