Cationic Effect on Pressure driven Spin-State Transition and cooperativity in Hybrid Perosvkites

TL;DR

This study uses first-principles calculations to show that cation choice in Fe-based hybrid perovskites influences pressure-induced spin-state transitions, with potential applications in sensors and memory devices.

Contribution

It reveals how A-site cation variation affects spin transition pressure and hysteresis in Fe-based MOF perovskites, demonstrating tunable spin-switching properties.

Findings

Pressure induces high-spin to low-spin transition in Fe(II) compounds.

Transition pressure and hysteresis width depend on A-site cation.

Electronic, magnetic, and optical properties change during transition.

Abstract

Hybrid or metal organic framework (MOF) perovskites of general composition, ABX$_3$, are known to show interesting properties which can lead to variety of technological applications. Our first principles study shows they are also potential candidates for exhibiting cooperative spin-state transitions upon application of external stimuli. We demonstrate this by considering two specific Fe-based MOF perovskites, namely Dimethylammonium Iron Formate, [CH$_{3}$NH$_{2}$CH$_{3}$][Fe(HCOO)$_3$] and Hydroxylammonium Iron Formate, [NH$_{3}$OH][Fe(HCOO)$_3$]. Both the compounds are found to undergo high-spin (S=2) to low-spin (S=0) transition at Fe(II) site upon application of moderate strength of hydrostatic pressure, along with large hysteresis. This spin-state transition is signaled by the changes in electronic, magnetic and optical properties. We find both the transition pressure and the width of the hysteresis to be strongly dependent of the choice of A-site cation, Dimethylammonium or Hydroxylammonium, implying tuning of spin-switching properties achievable by chemical variation of the amine cation in the structure. Our finding opens up novel functionalities in this family of materials of recent interest, which can have important usage in sensors and memory devices.