Phase transition tuning by Fe(III)/Co(III) substitution in switchable cyano-bridged perovskites: (C3H5N2)2[KFexCo1−x(CN)6]

Magdalena Rok; Marcin Moskwa; Andrzej Pawlukojć; Rafał Janicki; Iga Zuba; Piotr Zieliński; Paweł Sobieszczyk; Grażyna Bator

doi:10.1039/D0DT00615G

Phase transition tuning by Fe(iii)/Co(iii) substitution in switchable cyano-bridged perovskites: (C₃H₅N₂)₂[KFe_xCo_1−x(CN)₆]†

Magdalena Rok,

*^ab Marcin Moskwa,

^a Andrzej Pawlukojć,

^bc Rafał Janicki,

^a Iga Zuba,

^bc Piotr Zieliński,

^d Paweł Sobieszczyk

^d and Grażyna Bator

Author affiliations

* Corresponding authors

^a Faculty of Chemistry, University of Wroclaw, F. Joliot–Curie 14, 50-383 Wrocław, Poland
E-mail: magdalena.rok@chem.uni.wroc.pl

^b Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, Joliot–Curie 6, 141-980 Dubna, Russia

^c Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warszawa, Poland

^d The H. Niewodniczański Institute of Nuclear Physics PAS, Radzikowskiego 152, 31-342 Kraków, Poland

Abstract

The single-crystals of mixed (C₃H₅N₂)₂[KFe_xCo_1−x(CN)₆] crystals, with different ratios of x = 0, 0.29, 0.42, 0.51, 0.63, 0.70, 0.85, 1, have been grown from aqueous solutions. The thermal stability of the crystals has been determined using both DTA and TGA analysis. DSC has revealed sequences of structural phase transitions (PTs). We have found four solid phases for the crystals with concentrations x < 0.6 and three phases above these concentrations. The Fe(III) concentration has been estimated using the SEM technique. We have found the linear relationship of T_cversus the molar concentration of Fe(III) for the IV → III PT. Based on the obtained results, a phase diagram has been constructed. The mechanism of the structural PTs has been discussed based on the results of dielectric relaxation, NIR, IR and Raman spectroscopy

and X-ray measurements. Dielectric switching has been observed for all analysed mixed-crystals. All crystals exhibit ferroelastic properties.

Graphical abstract: Phase transition tuning by Fe(iii)/Co(iii) substitution in switchable cyano-bridged perovskites: (C3H5N2)2[KFexCo1−x(CN)6]

Supplementary files

Article information

DOI: https://doi.org/10.1039/D0DT00615G
Article type: Paper
Submitted: 18 Feb 2020
Accepted: 20 Mar 2020
First published: 20 Mar 2020

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Dalton Trans., 2020,49, 5503-5512

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Phase transition tuning by Fe(III)/Co(III) substitution in switchable cyano-bridged perovskites: (C₃H₅N₂)₂[KFe_xCo_1−x(CN)₆]

M. Rok, M. Moskwa, A. Pawlukojć, R. Janicki, I. Zuba, P. Zieliński, P. Sobieszczyk and G. Bator, Dalton Trans., 2020, 49, 5503 DOI: 10.1039/D0DT00615G

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