Principles of melting in hybrid organic–inorganic perovskite and polymorphic ABX3 structures

Four novel dicyanamide-containing hybrid organic–inorganic ABX3 structures are reported, and the thermal behaviour of a series of nine perovskite and non-perovskite [AB(N(CN)2)3] (A = (C3H7)4N, (C4H9)4N, (C5H11)4N; B = Co, Fe, Mn) is analyzed. Structure–property relationships are investigated by var...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2022-02, Vol.13 (7), p.2033-2042
Main Authors: Shaw, Bikash Kumar, Castillo-Blas, Celia, Thorne, Michael F, Ríos Gómez, María Laura, rest, Tom, Maria Diaz Lopez, Chater, Philip A, McHugh, Lauren N, Keen, David A, Bennett, Thomas D
Format: Article
Language:English
Subjects:
Cations
Chemistry
Cobalt
Iron
Manganese
Perovskites
Thermodynamic properties
Transition metals
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Summary:Four novel dicyanamide-containing hybrid organic–inorganic ABX3 structures are reported, and the thermal behaviour of a series of nine perovskite and non-perovskite [AB(N(CN)2)3] (A = (C3H7)4N, (C4H9)4N, (C5H11)4N; B = Co, Fe, Mn) is analyzed. Structure–property relationships are investigated by varying both A-site organic and B-site transition metal cations. In particular, increasing the size of the A-site cation from (C3H7)4N → (C4H9)4N → (C5H11)4N was observed to result in a decrease in Tm through an increase in ΔSf. Consistent trends in Tm with metal replacement are observed with each A-site cation, with Co < Fe < Mn. The majority of the melts formed were found to recrystallise partially upon cooling, though glasses could be formed through a small degree of organic linker decomposition. Total scattering methods are used to provide a greater understanding of the melting mechanism.
ISSN:2041-6520
2041-6539
DOI:10.1039/d1sc07080k