Photothermal studies of the room temperature photo-induced spin state change in the Fe(III)(salten)(mepepy) complex

Conflicting results have been reported with respect to the photoinduced switching of the magnetic properties of [FeIII(salten)]+ complexes [salten = 4‐azaheptamethylene‐1,7‐bis(salicylideneiminate)] coordinated by photoisomerizable ligands. In order to address this problem, two FeIII complexes [Fe(salten)(3‐azpy)]BPh4 (1) and [Fe(salten)(4‐azpy)]BPh4 (2) have been synthesized and characterized by various physicochemical methods (azpy = phenylazopyridine). Both 1 and 2 exhibit a low spin (S = 1/2) to high spin (HS, S = 5/2) transition in the solid state. In solution at room temperature both complexes are predominantly HS. Upon exposure to 310 (trans → cis) and 440 nm radiation (cis → trans) the free and coordinated 3‐ and 4‐azpy ligands undergo a reversible cis–trans isomerization. For 2 a corresponding reduction of the HS fraction 2 % is observed, whereas in 1 no effect is observed. Extensive DFT calculations, which employ different functionals and basis sets, explain this experimental result. The consequences of these findings with respect to the design of spin‐switchable iron(III) complexes with photoactive ligands are discussed.

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Fe^III Spin‐Crossover Complexes with Photoisomerizable Ligands: Experimental and Theoretical Studies on the Ligand‐Driven Light‐Induced Spin Change Effect

Bannwarth

Schmidt

Peters

et al. 2012

Eur J Inorg Chem

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Hysteretic spin crossover in isomeric iron(ii) complexes

et al. 2018

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Photothermal studies of the room temperature photo-induced spin state change in the Fe(III)(salten)(mepepy) complex

Cited by 2 publications

References 29 publications

Fe^III Spin‐Crossover Complexes with Photoisomerizable Ligands: Experimental and Theoretical Studies on the Ligand‐Driven Light‐Induced Spin Change Effect

Fe^III Spin‐Crossover Complexes with Photoisomerizable Ligands: Experimental and Theoretical Studies on the Ligand‐Driven Light‐Induced Spin Change Effect

Hysteretic spin crossover in isomeric iron(ii) complexes

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Photothermal studies of the room temperature photo-induced spin state change in the Fe(III)(salten)(mepepy) complex

Cited by 2 publications

References 29 publications

FeIII Spin‐Crossover Complexes with Photoisomerizable Ligands: Experimental and Theoretical Studies on the Ligand‐Driven Light‐Induced Spin Change Effect

FeIII Spin‐Crossover Complexes with Photoisomerizable Ligands: Experimental and Theoretical Studies on the Ligand‐Driven Light‐Induced Spin Change Effect

Hysteretic spin crossover in isomeric iron(ii) complexes

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Product

Resources

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Fe^III Spin‐Crossover Complexes with Photoisomerizable Ligands: Experimental and Theoretical Studies on the Ligand‐Driven Light‐Induced Spin Change Effect

Fe^III Spin‐Crossover Complexes with Photoisomerizable Ligands: Experimental and Theoretical Studies on the Ligand‐Driven Light‐Induced Spin Change Effect