Time-Resolved EPR Spectra of Photoexcited Copper Porphyrin

Iyudin, V. S.; Kandrashkin, Yu. E.; Воронкова, В. К.; Tyurin, V. S.; Kirichenko, E. N.

doi:10.1007/s00723-010-0184-2

Cited by 8 publications

(2 citation statements)

References 38 publications

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“…[159] Lately, the trip-quartet state of monomeric copperporphyrins was also observed. [160] Porphyrin dimers allow applying molecular guidelines similar to those outlined in Section 4 to fine-tune the exchange interaction between the porphyrin triplet and the metal doublet. These approaches have made it possible to create porphyrin complexes that, following photoexcitation, displayed triplet-doublet states in the weak and intermediate coupling regimes.…”

Section: Exploiting Metalloporphyrin Systemsmentioning

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: Exploiting Metalloporphyrin Systemsmentioning

confidence: 99%

Metalloporphyrins as Building Blocks for Quantum Information Science

Santanni,

Privitera

2024

Advanced Optical Materials

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“…Molecular architectures with two decoupled porphyrin sites could be used as platforms for generating high-multiplicity spin states for quantum information processing . Recent work on photoexcited chromophore–radical or chromophore–metal systems has shed light on a broad range of highly tunable trip–doublet and quartet states with potential applications in molecular spintronics and as multilevel qudit systems. − Therefore, a molecule that allows the formation of a photogenerated triplet state that is weakly coupled to a redox active, tunable, ground-state porphyrin unit with a metal binding site would be a versatile platform for investigating high-multiplicity spin states. In this work, we investigate the delocalization of the photogenerated triplet state in a tetramethylbiphenyl-linked Zn-porphyrin dimer using transient cw-EPR and 1 H Mims ENDOR spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Charge and Spin Transfer Dynamics in a Weakly Coupled Porphyrin Dimer

Kopp,

Redman,

Rončević

et al. 2024

J. Am. Chem. Soc.

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The dynamics of electron and spin transfer in the radical cation and photogenerated triplet states of a tetramethylbiphenyl-linked zinc-porphyrin dimer were investigated, so as to test the relevant parameters for the design of a single-molecule spin valve and the creation of a novel platform for the photogeneration of high-multiplicity spin states. We used a combination of multiple techniques, including variabletemperature continuous wave EPR, pulsed proton electron−nuclear double resonance (ENDOR), transient EPR, and optical spectroscopy. The conclusions are further supported by density functional theory (DFT) calculations and comparison to reference compounds. The low-temperature cw-EPR and room-temperature near-IR spectra of the dimer monocation demonstrate that the radical cation is spatially localized on one side of the dimer at any point in time, not coherently delocalized over both porphyrin units. The EPR spectra at 298 K reveal rapid hopping of the radical spin density between both sites of the dimer via reversible intramolecular electron transfer. The hyperfine interactions are modulated by electron transfer and can be quantified using ENDOR spectroscopy. This allowed simulation of the variable-temperature cw-EPR spectra with a two-site exchange model and provided information on the temperature-dependence of the electron transfer rate. The electron transfer rates range from about 10.0 MHz at 200 K to about 53.9 MHz at 298 K. The activation enthalpies Δ ‡ H of the electron transfer were determined as Δ ‡ H = 9.55 kJ mol −1 and Δ ‡ H = 5.67 kJ mol −1 in a 1:1:1 solvent mixture of CD 2 Cl 2 /toluene-d 8 /THF-d 8 and in 2-methyltetrahydrofuran, respectively, consistent with a Robin−Day class II mixed valence compound. These results indicate that the interporphyrin electronic coupling in a tetramethylbiphenyl-linked porphyrin dimer is suitable for the backbone of a single-molecule spin valve. Investigation of the spin density distribution of the photogenerated triplet state of the Zn-porphyrin dimer reveals localization of the triplet spin density on a nanosecond time scale on one-half of the dimer at 20 K in 2-methyltetrahydrofuran and at 250 K in a polyvinylcarbazole film. This establishes the porphyrin dimer as a molecular platform for the formation of a localized, photogenerated triplet state on one porphyrin unit that is coupled to a second redox-active, ground-state porphyrin unit, which can be explored for the formation of high-multiplicity spin states.

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Stimulated Electron Spin Polarization in Strongly Coupled Triplet–Doublet Spin Pairs

Kandrashkin

Est

2011

Appl Magn Reson

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Time-Resolved EPR Spectra of Photoexcited Copper Porphyrin

Cited by 8 publications

References 38 publications

Metalloporphyrins as Building Blocks for Quantum Information Science

Metalloporphyrins as Building Blocks for Quantum Information Science

Charge and Spin Transfer Dynamics in a Weakly Coupled Porphyrin Dimer

Stimulated Electron Spin Polarization in Strongly Coupled Triplet–Doublet Spin Pairs

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