Study of Anisotropic Interfacial Electron Transfer Across a Semiconductor/Solution Interface by Time‐Resolved EPR Spectroscopy

Akiyama, Kazuo; Hashimoto, Shinji; Tojo, Sachiko; Ikoma, Tadaaki; Tero‐Kubota, Shozo; Majima, Tetsuro

doi:10.1002/anie.200461681

Cited by 3 publications

(1 citation statement)

References 28 publications

(32 reference statements)

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“…This paper reports the first time-resolved (TR) EPR study of breathing crystals. TR EPR is most often used for studying photoinduced reactions in liquids at ambient temperatures or in frozen solutions; − however, as we show here, it can also be used for monitoring transient EPR signals in solid-phase molecular magnets arising during spin state switching/relaxation on the nanosecond time scale. To enhance spectral resolution, we use high-field W-band TR EPR (94 GHz).…”

Section: Introductionmentioning

confidence: 91%

W-Band Time-Resolved Electron Paramagnetic Resonance Study of Light-Induced Spin Dynamics in Copper–Nitroxide-Based Switchable Molecular Magnets

et al. 2012

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Molecular magnets Cu(hfac)(2)L(R) represent a new type of photoswitchable materials based on exchange-coupled clusters of copper(II) with stable nitroxide radicals. It was found recently that the photoinduced spin state of these compounds is metastable on the time scale of hours at cryogenic temperatures, similar to the light-induced excited spin state trapping phenomenon well-known for many spin-crossover compounds. Our previous studies have shown that electron paramagnetic resonance (EPR) in continuous wave (CW) mode allows for studying the light-induced spin state conversion and relaxation in the Cu(hfac)(2)L(R) family. However, light-induced spin dynamics in these compounds has not been studied on the sub-second time scale so far. In this work we report the first time-resolved (TR) EPR study of light-induced spin state switching and relaxation in Cu(hfac)(2)L(R) with nanosecond temporal resolution. To enhance spectral resolution we used high-frequency TR EPR at W-band (94 GHz). We first discuss the peculiarities of applying TR EPR to the solid-phase compounds Cu(hfac)(2)L(R) at low (liquid helium) temperatures and approaches developed for photoswitching/relaxation studies. Then we analyze the kinetics of the excited spin state at T = 5-21 K. It has been found that the photoinduced spin state is formed at time delays shorter than 100 ns. It has also been found that the observed relaxation of the excited state is exponential on the nanosecond time scale, with the decay rate depending linearly on temperature. We propose and discuss possible mechanisms of these processes and correlate them with previously obtained CW EPR data.

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Section: Introductionmentioning

confidence: 91%

W-Band Time-Resolved Electron Paramagnetic Resonance Study of Light-Induced Spin Dynamics in Copper–Nitroxide-Based Switchable Molecular Magnets

et al. 2012

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Photoinduced Triplet States of Photoconductive TTF Derivatives Including a Fluorescent Group

Furukawa¹,

Sugishima²,

Fujiwara³

et al. 2011

Chemistry Letters

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The spin dynamics of photoconductive tetrathiafulvalene (TTF) derivatives containing 2,5-diphenyl-1,3,4-oxadiazole (PPD) was examined using time-resolved electron spin resonance (TR-ESR) spectroscopy. TR-ESR signals of a frozen solution sample under visible excitation were attributed to the excited triplet state T1, which was populated via intersystem crossing from the excited singlet state S1 as confirmed by TR-ESR spectral simulations. From DFT calculations, the spin-density distribution of the T1 state was found to be concentrated around the linker between the TTF and PPD molecules.

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可視光応答型酸化チタンにおける活性種

Tero‐Kubota¹

2005

Electrochemistry

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Study of Anisotropic Interfacial Electron Transfer Across a Semiconductor/Solution Interface by Time‐Resolved EPR Spectroscopy

Cited by 3 publications

References 28 publications

W-Band Time-Resolved Electron Paramagnetic Resonance Study of Light-Induced Spin Dynamics in Copper–Nitroxide-Based Switchable Molecular Magnets

W-Band Time-Resolved Electron Paramagnetic Resonance Study of Light-Induced Spin Dynamics in Copper–Nitroxide-Based Switchable Molecular Magnets

Photoinduced Triplet States of Photoconductive TTF Derivatives Including a Fluorescent Group

可視光応答型酸化チタンにおける活性種

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