Journal
JOURNAL OF MATERIALS CHEMISTRY C
Volume 9, Issue 25, Pages 8051-8056Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1tc01966j
Keywords
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Funding
- Swiss National Science Foundation [P2BEP2_188253]
- Royal Society University Research Fellowship
- Swiss National Science Foundation (SNF) [P2BEP2_188253] Funding Source: Swiss National Science Foundation (SNF)
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The study demonstrates a pressure-induced orbital reordering phase transition in [(CH3)(2)NH2]Cu(HCOO)(3) above 5.20 GPa, driven primarily by unconventional octahedral tilts and shifts in the framework. This transition differs from previously reported Jahn-Teller switching in coordination polymers, and may lead to undiscovered orbital reorientation phenomena in this family of materials.
Through in situ, high-pressure X-ray diffraction experiments we have shown that the homoleptic perovskite-like coordination polymer [(CH3)(2)NH2]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 [(CH3)(2)NH2]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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