Effect of intermacrocyclic interactions: Modulation of metal spin-state in oxo/hydroxo/fluoro-bridged diiron(III)/dimanganese(III) porphyrin dimers

Sil, Debangsu; Khan, Firoz Shah Tuglak; Rath, Sankar Prasad

doi:10.1016/bs.adioch.2022.08.002

Advances in Inorganic Chemistry

2023

DOI: 10.1016/bs.adioch.2022.08.002

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Effect of intermacrocyclic interactions: Modulation of metal spin-state in oxo/hydroxo/fluoro-bridged diiron(III)/dimanganese(III) porphyrin dimers

Debangsu Sil

Firoz Shah Tuglak Khan

Sankar Prasad Rath

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Cited by 3 publications

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Stable Dication Diradicals of Triply Fused Metallo Chlorin‐Porphyrin Heterodimers: Impact of the Bridge on the Control of Spin Coupling to Reactivity

Shah,

Pandit,

Garribba

et al. 2023

Chemistry A European J

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Herein we report an unexpected rearrangement, controlled by the nature of bridge, leading to the formation of novel, remarkably stable triply‐fused dinickel(II)/dicopper(II) chlorin‐porphyrin dication diradical heterodimers in excellent yields in which dipyrromethane‐bridge gets completely fused between two porphyrin macrocycles with two new C–C and one C–N bonds. Two macrocycles exhibit extensive π‐conjugation through the bridge which results in an antiferromagnetic coupling between the two π‐cation radicals. In addition, the macrocyclic distortion also favours a rare intramolecular ferromagnetic interaction between the Cu(II) and π‐cation radical spins to form a triplet state. The structural and electronic perturbation in the non‐conjugated dication diradical possibly enables the bridging pyrrolic nitrogen to undergo a nucleophilic attack at the nearby β‐carbon of the porphyrin π‐cation radical with a computed free energy barrier of more than 20 kcal/mol which has been supplied in the form of reflux condition to initiate such rearrangement process. UV‐vis, EPR and ESI‐MS spectroscopies were utilized to monitor the rearrangement process in situ in order to identify key reactive intermediates leading to such an unusual transformation.

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Stable Dication Diradicals of Triply Fused Metallo Chlorin‐Porphyrin Heterodimers: Impact of the Bridge on the Control of Spin Coupling to Reactivity

Shah,

Pandit,

Garribba

et al. 2023

Chemistry A European J

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Spin‐Flip via Subtle Electronic Perturbation in Axially Ligated Diiron(III) Porphyrin Dimer

Chakraborty,

Ghosh,

Awasthi

et al. 2024

Chemistry A European J

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Spin state switching in the metal center is a crucial phenomenon in many enzymatic reactions in biology. In the current work, the spin state transition of iron(III) from high to intermediate via an admixed state is observed upon a subtle electronic perturbations to the sulphonate moieties coordinated axially to a diiron(III)porphyrin dimer. While electron‐donating substituents stabilize the high‐spin state of iron, strongly electron‐withdrawing groups stabilize an intermediate‐spin state, whereas the moderate electron‐withdrawing nature of axial ligands resulted in an admixed state. Electronic structures have been confirmed utilizing single‐crystal X‐ray structure analysis, Mössbauer, magnetic, EPR, and 1H NMR spectroscopic investigations. The 1H NMR spectra are found to be characteristic of the spin state of the iron. The signals of the high and intermediate‐spin complexes follow the Curie and anti‐Curie temperature dependence, respectively, whereas the admixed‐spin state of iron displays significant curvature of the lines in the Curie plot. An extensive DFT analysis displays a linear correlation between the Fe‐O distance and the spin density over the oxygen atom, as well as the Fe‐Npor distance for the complexes. Thus, a slight electronic perturbation at a far end of the diheme resulted in a large change in the electronic structures with a spin‐flip.

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Reversible open–closed conformational switching of nano-size metalloporphyrin dimers triggered by light and temperature

Shah,

Singh,

Goswami

et al. 2024

Dalton Trans.

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Effect of intermacrocyclic interactions: Modulation of metal spin-state in oxo/hydroxo/fluoro-bridged diiron(III)/dimanganese(III) porphyrin dimers

Cited by 3 publications

References 199 publications

Stable Dication Diradicals of Triply Fused Metallo Chlorin‐Porphyrin Heterodimers: Impact of the Bridge on the Control of Spin Coupling to Reactivity

Stable Dication Diradicals of Triply Fused Metallo Chlorin‐Porphyrin Heterodimers: Impact of the Bridge on the Control of Spin Coupling to Reactivity

Spin‐Flip via Subtle Electronic Perturbation in Axially Ligated Diiron(III) Porphyrin Dimer

Reversible open–closed conformational switching of nano-size metalloporphyrin dimers triggered by light and temperature

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