The pressure response of Jahn–Teller-distorted Prussian blue analogues
| العنوان: | The pressure response of Jahn–Teller-distorted Prussian blue analogues |
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| المؤلفون: | Boström, Hanna L. B., 1991, Cairns, Andrew B., Chen, Muzi, Daisenberger, Dominik, Ridley, Christopher J., Funnell, Nicholas P. |
| المصدر: | Chemical Science. 15(9):3155-3164 |
| الوصف: | Jahn–Teller (JT) distorted CuII-containing compounds often display interesting structural and functional behaviour upon compression. We use high-pressure X-ray and neutron diffraction to investigate four JT-distorted Prussian blue analogues: Cu[Co(CN)6]0.67, CuPt(CN)6, and ACuCo(CN)6 (A = Rb, Cs), where the first two were studied in both their hydrated and dehydrated forms. All compounds are less compressible than the JT-inactive MnII-based counterparts, indicating a coupling between the electronic and mechanical properties. The effect is particularly strong for Cu[Co(CN)6]0.67, where the local JT distortions are uncorrelated (so-called orbital disorder). This sample amorphises at 0.5 GPa when dehydrated. CuPt(CN)6 behaves similarly to the MnII-analogues, with phase transitions at around 1 GPa and low sensitivity to water. For ACuCo(CN)6, the JT distortions reduce the propensity for phase transitions, although RbCuCo(CN)6 transitions to a new phase (P2/m) around 3 GPa. Our results have a bearing on both the topical Prussian blue analogues and the wider field of flexible frameworks. |
| وصف الملف: | |
| URL الوصول: | https://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-226623 https://doi.org/10.1039/d3sc06912e |
| قاعدة البيانات: | SwePub |
| تدمد: | 20416520 20416539 |
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| DOI: | 10.1039/d3sc06912e |