Second‐Harmonic and Terahertz Generation in a Prussian‐Blue Analogue

Ould-Hamouda, Amine; Iazzolino, Antonio; Tokoro, Hiroko; Ohkoshi, Shin‐ichi; Freysz, É.

doi:10.1002/ejic.201700980

Cited by 3 publications

(1 citation statement)

References 22 publications

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“…A check of the CCDC database reveals that only 6 of the 78 unique [Mn(R-Sal 2 323)] + complexes published before 2021 crystallize adventitiously in a chiral space group, − with a seventh example targeted by introduction of a chiral anion . The interplay between SCO and chirality − is increasingly recognized as an important route to switchable nonlinear optical (NLO) materials ,− and spin-state dependent changes in optical activity may also constitute an economic and low energy route to follow SCO in sensing applications. Here we use circular dichroism to confirm the spontaneous resolution in the case of the ClO 4 – complex ( 1 ) and to demonstrate that the complex is stable toward racemization in solution.…”

Section: Introductionmentioning

confidence: 99%

Homochiral Mn³⁺ Spin-Crossover Complexes: A Structural and Spectroscopic Study

et al. 2022

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Structural, magnetic, and spectroscopic data on a Mn 3+ spin-crossover complex with Schiff base ligand 4-OMe-Sal 2 323, isolated in crystal lattices with five different counteranions, are reported. Complexes of [Mn(4-OMe-Sal 2 323)]X where X = ClO 4 – ( 1 ), BF 4 – ( 2 ), NO 3 – ( 3 ), Br – ( 4 ), and I – ( 5 ) crystallize isotypically in the chiral orthorhombic space group P 2 1 2 1 2 with a range of spin state preferences for the [Mn(4-OMe-Sal 2 323)] + complex cation over the temperature range 5–300 K. Complexes 1 and 2 are high-spin, complex 4 undergoes a gradual and complete thermal spin crossover, while complexes 3 and 5 show stepped crossovers with different ratios of spin triplet and quintet forms in the intermediate temperature range. High-field electron paramagnetic resonance was used to measure the zero-field splitting parameters associated with the spin triplet and quintet states at temperatures below 10 K for complexes 4 and 2 with respective values: D S =1 = +23.38(1) cm –1 , E S =1 = +2.79(1) cm –1 , and D S =2 = +6.9(3) cm –1 , with a distribution of E parameters for the S = 2 state. Solid-state circular dichroism (CD) spectra on high-spin complex 1 at room temperature reveal a 2:1 ratio of enantiomers in the chiral conglomerate, and solution CD measurements on the same sample in methanol show that it is stable toward racemization. Solid-state UV–vis absorption spectra on high-spin complex 1 and mixed S = 1/ S = 2 sample 5 reveal different intensities at higher energies, in line with the different electronic composition. The statistical prevalence of homochiral crystallization of [Mn(4-OMe-Sal 2 323)] + in five lattices with different achiral counterions suggests that the chirality may be directed by the 4-OMe-Sal 2 323 ligand.

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Section: Introductionmentioning

confidence: 99%

Homochiral Mn³⁺ Spin-Crossover Complexes: A Structural and Spectroscopic Study

et al. 2022

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Rational Direct Synthesis of RbMnFe Nanoparticles (RbMnFe = Rb_xMn[Fe(CN)₆]_(2+x)/3·nH₂O Prussian Blue Analogue)

Daro

Marchivie

et al. 2022

Inorg. Chem.

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In this paper, we report the chemical strategy followed to obtain, in a direct way, nanoparticles of the Rb x Mn[Fe(CN)6](x+2)/3·nH2O (RbMnFe) Prussian blue analogue with the aim of keeping the switching ability of this compound at the nanoscale. The switching properties come from a reversible electron transfer between the iron and manganese ions and depends on the rubidium content in the structure that has to be higher than 0.6. Despite the multifunctionality of this family of compounds and its interest in various applications, no systematic studies were performed to obtain well-defined nanoparticles. This paper relates to such an investigation. To draw relationship between size reduction, composition, and switching properties, a special attention was brought to the determination of the composition through elemental analysis and structure refinement of powder X-ray diffraction patterns together with infrared spectroscopy and elemental analysis. Several chemical parameters were explored to control both the size reduction and the composition following a direct synthetic approach. The results show that the smaller the particles, the lower the rubidium content. This observation might prevent the observation of switching properties on very small particles. Despite this antagonist effect, we achieved switchable particles of around 200 nm without any use of surfactant. Moreover, the size reduction is associated with the observation of the electron transfer down to 52% of rubidium in the nanoparticles against 64% in microparticles. This work is of particular interest in processing such nanoparticles into devices.

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