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Pressure-induced Jahn–Teller switch in the homoleptic hybrid perovskite [(CH(3))(2)NH(2)]Cu(HCOO)(3): orbital reordering by unconventional degrees of freedom
Through in situ, high-pressure X-ray diffraction experiments we have shown that the homoleptic perovskite-like coordination polymer [(CH(3))(2)NH(2)]Cu(HCOO)(3) undergoes a pressure-induced orbital reordering phase transition above 5.20 GPa. This transition is distinct from previously reported Jahn–...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8246535/ https://www.ncbi.nlm.nih.gov/pubmed/34277008 http://dx.doi.org/10.1039/d1tc01966j |
Sumario: | Through in situ, high-pressure X-ray diffraction experiments we have shown that the homoleptic perovskite-like coordination polymer [(CH(3))(2)NH(2)]Cu(HCOO)(3) undergoes a pressure-induced orbital reordering phase transition above 5.20 GPa. This transition is distinct from previously reported Jahn–Teller switching in coordination polymers, which required at least two different ligands that crystallize in a reverse spectrochemical series. We show that the orbital reordering phase transition in [(CH(3))(2)NH(2)]Cu(HCOO)(3) is instead primarily driven by unconventional octahedral tilts and shifts in the framework, and/or a reconfiguration of A-site cation ordering. These structural instabilities are unique to the coordination polymer perovskites, and may form the basis for undiscovered orbital reorientation phenomena in this broad family of materials. |
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