Probing the local structure of Prussian blue electrodes by <sup>113</sup>Cd NMR spectroscopy

Flambard, Alexandrine; Sugahara, Akira; De, Siddhartha; Okubo, Masashi; Yamada, Atsuo; Lescouëzec, Rodrigue

doi:10.1039/c7dt00728k

Cited by 10 publications

(5 citation statements)

References 38 publications

(31 reference statements)

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“…In previous works, we showed that NMR active nuclei of diamagnetic ions such as 113 Cd could be used as local probe to access accurate information on the local structure and electronic states of paramagnetic cyanide‐based compounds [23] . For example, we showed that 113 Cd NMR was efficient in revealing the electronic state changes occurring upon reversible Li + intercalation in nanoporous CdFe Prussian blue analogues (PBAs) [23c] . This information is made accessible in a M−CN−Cd pair as the changes of electronic/magnetic state on the M ion can be felt by the diamagnetic NMR active Cd(II) ion.…”

Section: Resultsmentioning

confidence: 99%

Molecular Magnetic Materials Based on {Co^III(Tp*)(CN)₃}⁻ Cyanidometallate: Combined Magnetic, Structural and ⁵⁹Co NMR Study

Flambard

et al. 2022

Chemistry A European J

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The cyanidocobaltate of formula fac-PPh 4 [Co III -( Me2 Tp)(CN) 3 ] • CH 3 CN (1) has been used as a metalloligand to prepare polynuclear magnetic complexes ( Me2 Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate). The association of 1 with in situ prepared [Fe II (bik) ). These compounds were structurally characterized via single crystal X-ray analysis and their spectroscopic (FTIR, UV-Vis and 59 Co NMR) properties and magnetic behaviours were also investigated. Bulk magnetic susceptibility measurements reveal that 1 is diamagnetic and 3 is paramagnetic through-out the explored temperature range, whereas 2 exhibits sharp spin transition centered at ca. 292 K. Compound 2 also exhibits photomagnetic effects at low temperature, selective light irradiations allowing to promote reversibly and repeatedly low-spin⇔high-spin conversion. Besides, the diamagnetic nature of the Co(III) building block allows us studying these compounds by means of 59 Co NMR spectroscopy. Herein, a 59 Co chemical shift has been used as a magnetic probe to corroborate experimental magnetic data obtained from bulk magnetic susceptibility measurements. An influence of the magnetic state of the neighbouring atoms is observed on the 59 Co NMR signals. Moreover, for the very first time, 59 Co NMR technique has been successfully introduced to investigate molecular materials with distinct magnetic properties.

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Section: Resultsmentioning

confidence: 99%

Molecular Magnetic Materials Based on {Co^III(Tp*)(CN)₃}⁻ Cyanidometallate: Combined Magnetic, Structural and ⁵⁹Co NMR Study

Flambard

et al. 2022

Chemistry A European J

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“…[85] The larger negative chemical shift is likely caused by the fact that the more the Fe paramagnetic ions are connected to the intercalation ions, the greater the distribution of the spin density on the nitrogen ions. [86] This also indicates the existence of the designed Fe-N interaction. The obvious 4.1 ppm and weak 3.5 ppm peaks are attributed to physical adsorption of water on the material surface.…”

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confidence: 81%

Switching Optimally Balanced Fe–N Interaction Enables Extremely Stable Energy Storage

Zhao

Zhang

Liu

et al. 2022

Energy & Environ Materials

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“…With advancements in molecular bistable systems, their characterization methods, − and various device fabrication techniques and strategies, ,,, the hidden potential of field is being realized and will lead to many groundbreaking findings in the field of molecular devices and nanodevices.…”

Section: Future Outlookmentioning

confidence: 99%

Realm of Spin State Switching Materials: Toward Realization of Molecular and Nanoscale Devices

Kamilya,

Dey,

Kaushik

et al. 2024

Chem. Mater.

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For various technological applications involving the design of molecular-and nanoscale devices, spin crossover (SCO) materials are a way forward owing to an ability to have a readout in the form of distinct changes in physical properties accompanying the stimuli-responsive spin-state modifications. In particular, ironbased molecular SCO systems are of great interest as they have shown vast potential applications in the design of functional devices, including sensors and electrical, optical, mechanical, spintronic, memory storage, and processing devices. Due to the inherent fragility of SCO systems, several factors, such as substrate selection, electrode materials (in the case of electronic devices), and molecule−substrate interactions, must be carefully considered while integrating SCO systems into functional devices. To ensure reliable device performance, the compatibility of SCO complexes with the techniques used to fabricate devices is also crucial. Considering these factors, the major aim of this Perspective is to concisely represent a part of our research work on this broad up-and-coming topic, mentioning the relevance of spin crossover materials, and provide an overview to the reader about the recent developments, achievements, and advancements of micro-and nanoscale devices based on the phenomena of spin-state switching, which in turn is highly versatile. A particular emphasis is given to the SCO systems used for thin films, nanoparticles, and molecule-based devices, highlighting the challenges and prospects associated with each approach.

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Probing the local structure of Prussian blue electrodes by ¹¹³Cd NMR spectroscopy

Abstract: We demonstrate that 113Cd NMR is a potent technique to monitor the local electronic and structural states of the Prussian blue electrode during Li+ intercalation, providing an atomic-scale insight into the reaction mechanism.

Cited by 10 publications

References 38 publications

Molecular Magnetic Materials Based on {Co^III(Tp*)(CN)₃}⁻ Cyanidometallate: Combined Magnetic, Structural and ⁵⁹Co NMR Study

Molecular Magnetic Materials Based on {Co^III(Tp*)(CN)₃}⁻ Cyanidometallate: Combined Magnetic, Structural and ⁵⁹Co NMR Study

Switching Optimally Balanced Fe–N Interaction Enables Extremely Stable Energy Storage

Realm of Spin State Switching Materials: Toward Realization of Molecular and Nanoscale Devices

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Probing the local structure of Prussian blue electrodes by 113Cd NMR spectroscopy

Abstract: We demonstrate that 113Cd NMR is a potent technique to monitor the local electronic and structural states of the Prussian blue electrode during Li+ intercalation, providing an atomic-scale insight into the reaction mechanism.

Cited by 10 publications

References 38 publications

Molecular Magnetic Materials Based on {CoIII(Tp*)(CN)3}− Cyanidometallate: Combined Magnetic, Structural and 59Co NMR Study

Molecular Magnetic Materials Based on {CoIII(Tp*)(CN)3}− Cyanidometallate: Combined Magnetic, Structural and 59Co NMR Study

Switching Optimally Balanced Fe–N Interaction Enables Extremely Stable Energy Storage

Realm of Spin State Switching Materials: Toward Realization of Molecular and Nanoscale Devices

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Probing the local structure of Prussian blue electrodes by ¹¹³Cd NMR spectroscopy

Molecular Magnetic Materials Based on {Co^III(Tp*)(CN)₃}⁻ Cyanidometallate: Combined Magnetic, Structural and ⁵⁹Co NMR Study

Molecular Magnetic Materials Based on {Co^III(Tp*)(CN)₃}⁻ Cyanidometallate: Combined Magnetic, Structural and ⁵⁹Co NMR Study