Ferromagnetic Coupling in Oxidovanadium(IV)–Porphyrin Radical Dimers

Singh, Akhil Kumar; Usman, Mohammad; Sarkar, Sabyasachi; Sciortino, Giuseppe; Kumar, Devesh; Garribba, Eugenio; Rath, Sankar Prasad

doi:10.1021/acs.inorgchem.1c02331

Cited by 11 publications

(3 citation statements)

References 104 publications

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“…Exchange interactions can be further increased by exploiting the strategy reported by Singh et al, [ 98 ] who developed a vanadyl‐porphyrin dimer with the two units bonded by the cis ‐ or trans ‐alkenyl group. Two radical spins were introduced via reaction with AgClO 4 as an oxidant agent, promoting strong coupling interactions.…”

Section: Porphyrin‐based Quantum Logic Gatesmentioning

confidence: 99%

Metalloporphyrins as Building Blocks for Quantum Information Science

Santanni,

Privitera

2024

Advanced Optical Materials

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The intrinsic quantum nature of molecules opens exciting opportunities for developing the field of quantum information science. In this context, porphyrins stand out as ideal building blocks for quantum technologies thanks to their unique optical and electrical properties as well as their capacity to accommodate metal atoms and ions. This review bridges the chemistry and physics of porphyrins, providing an overview of recent advances in porphyrin‐based molecular qubits. Starting from qubits, the review explores the potential of porphyrin units to combine, leading to the formation of quantum logic gates and hierarchical higher‐dimensional structures. Next, the exploitation of porphyrins' unique photophysical properties for realizing long‐lived high spin states is examined. These states are promising for the photogeneration of multi‐level systems and the optical initialization and control of molecular qubits. With a critical eye on the current state‐of‐the‐art, the review elucidates the future perspectives of porphyrins for advancing quantum technologies.

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Section: Porphyrin‐based Quantum Logic Gatesmentioning

confidence: 99%

Metalloporphyrins as Building Blocks for Quantum Information Science

Santanni,

Privitera

2024

Advanced Optical Materials

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“…This turn is caused by the steric interactions of the heterocycle with b-pyrrolic substituents, which is common for meso-ethenyl substituted porphyrins. [33,34] Nevertheless, the sensor properties of the conjugates may rely on the increased interactions between the porphyrin dye and the heterocycle receptor in the excited state. [33,35] The dramatic spectral change of the conjugate with TBA 2 was quite different.…”

mentioning

confidence: 99%

“…[33,34] Nevertheless, the sensor properties of the conjugates may rely on the increased interactions between the porphyrin dye and the heterocycle receptor in the excited state. [33,35] The dramatic spectral change of the conjugate with TBA 2 was quite different. The new strong absorption band arose at 509 nm.…”

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confidence: 99%

Synthesis of β-Octaethylporphyrin Conjugates with Nitrogen and Sulfur Containing Heterocycles

Shkirdova¹,

Orlova²,

Ponomarev³

et al. 2021

MHC

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Сonjugates of Ni(II) b-octaethylporphyrin with nitrogen and sulfur containing heterocycles were obtained by meso-functionalization of the porphyrin. The meso-functionalization of Ni(II) b-octaethylporphyrin was performed by the Vilsmeier-Haack formylation reaction, followed by the Knoevenagel reaction of Ni(II) meso-formylb-octaethylporphyrin with CH-acids: malonic ester, thiohydantoin, and thiobarbituric acid. The product of condensation of the porphyrin with malonic ester was cyclized with hydrazine to the corresponding porphyrin conjugate with pyrazolidine-3,5-dione. The optical spectra of the obtained new dyes are modified compared to that of the initial compounds. The spectral changes of the porphyrin conjugate with thiobarbituric acid are particularly dramatic reflecting the considerable interaction between tetrapyrrolic and heterocyclic chromophores in the molecule.

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Unusual Stabilisation of Remarkably Bent Tetra‐Cationic Tetra‐radical Intermolecular Fe(III) μ‐Oxo Tetranuclear Complexes

Sarkar,

Tiwari,

Samanta

et al. 2024

Angewandte Chemie

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A hitherto unknown series of air stable, π‐conjugated, remarkably bent tetra‐cation tetra‐radical intermolecular Fe(III) µ‐oxo tetranuclear complex, isolated from the dication diradical diiron(III) porphyrin dimers, has been synthesised and spectroscopically characterised along with single crystal X‐ray structure determination of two such molecules. These species facilitate long‐range charge/radical delocalisation through the bridge across the entire tetranuclear unit manifesting an unusually intense NIR band. Assorted spin states of Fe(III) centres are stabilised within these unique tetranuclear frameworks: terminal six‐coordinate iron centres stabilise the admixed intermediate spin states while the central five‐coordinate iron centres stabilise the high‐spin states. Variable temperature magnetic susceptibility measurements indicated strong antiferromagnetic coupling for the Fe(III)‐O‐Fe(III) unit while the exchange interactions between the Fe centres and the porphyrin π‐cation radicals are weaker as supported both by magnetic data and DFT calculations. The nature of orbital overlap between the SOMOs of Fe(III) and π* orbital of the porphyrin was found to rationalise the observed exchange coupling, establishing such a complex magnetic exchange in this tetranuclear model with a significant bioinorganic relevance.

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Ferromagnetic Coupling in Oxidovanadium(IV)–Porphyrin Radical Dimers

Cited by 11 publications

References 104 publications

Metalloporphyrins as Building Blocks for Quantum Information Science

Metalloporphyrins as Building Blocks for Quantum Information Science

Synthesis of β-Octaethylporphyrin Conjugates with Nitrogen and Sulfur Containing Heterocycles

Unusual Stabilisation of Remarkably Bent Tetra‐Cationic Tetra‐radical Intermolecular Fe(III) μ‐Oxo Tetranuclear Complexes

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