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Structural phase transitions coupled with prominent dielectric anomalies and dielectric relaxation in [(CH3)3NH]2[KCo(CN)6] and mixed [(CH3)3NH]2[KFexCo1−x(CN)6] double perovskite hybrids

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Abstract

The crystals of pure [(CH3)3NH]2[KFe(CN)6] (TrMAFe) and [(CH3)3NH]2[KCo(CN)6] (TrMACo) as well as their mixed crystals (TrMAFexCo1−x), with different ratios of x = 0, 0.12, 0.18, 0.49, 0.56, 0.73, 0.81, 1.0, have been grown from aqueous solutions. The structure of TrMACo has been determined at 360 K to be cubic (Fm[3 with combining macron]m). In phase II (100 K), the TrMACo crystal is monoclinic (C2/c). The thermal stability of the pure and mixed crystals has been determined by using both DTA and TGA. Based on the DSC results, we have found a single phase transition (PT) for both pure and mixed crystals. The Fe(III) concentration was estimated by using the SEM technique. We have found a linear relationship between the PT temperature (Tc) and the molar concentration of Fe(III). Based on the obtained results, a phase diagram has been constructed. The mechanism of the structural PT has been discussed based on the results of dielectric relaxation and 1H NMR and X-ray spectroscopy measurements. The results confirmed that the PT mechanism of both pure and mixed crystals is related to the change in the dynamic state of the TrMA+ cations. The dielectric activation energy changes linearly with the mole fraction ranking from 35 to 38 kJ mol−1, for the mixed crystals.

Graphical abstract: Structural phase transitions coupled with prominent dielectric anomalies and dielectric relaxation in [(CH3)3NH]2[KCo(CN)6] and mixed [(CH3)3NH]2[KFexCo1−x(CN)6] double perovskite hybrids

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Supplementary files

Article information


Submitted
10 Dec 2019
Accepted
06 Jan 2020
First published
06 Jan 2020

Dalton Trans., 2020, Advance Article
Article type
Paper

Structural phase transitions coupled with prominent dielectric anomalies and dielectric relaxation in [(CH3)3NH]2[KCo(CN)6] and mixed [(CH3)3NH]2[KFexCo1−x(CN)6] double perovskite hybrids

M. Rok, B. Zarychta, M. Moskwa, B. Dziuk, W. Medycki and G. Bator, Dalton Trans., 2020, Advance Article , DOI: 10.1039/C9DT04703D

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